Glycerol Acetylation 1

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1. Partially acetylated polyhydroxylic compounds

No Inventor data available
From Ger.DE 122145 , Language: Unavailable, Database: CAPLUS
When completely acetylated hydroxylic compounds are heated with the unaltered substance, a reaction occurs between
the two, resulting in the formation of a partially acetylated derivative. When triacetin and glycerol in equal proportion by
weight are heated for several hours at 200°, the chief product of reaction is monoacetin. Monoacetylresorcinol results
from resorcinol (2 parts) and diacetylresorcinol (3 parts) when the mixture is heated at 170°. The monoacetyl derivative
of pyrogallol is produced under similar conditions from a mixture of pyrogallol and its triacetyl compound. Anthrapurpurin
and its triacetyl compound yield the corresponding diacetyl derivative.
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Copyright © 2018 American Chemical Society (ACS). All Rights Reserved.
2. Estimation of glycerol in soap lyes and crude glycerol

By Hehner, O.
From Journal of the Society of Chemical Industry, London8, 4-9. Language: Unavailable, Database: CAPLUS
The author has investigated the chief methods in use for the estimation of glycerol in order to test their accuracy. He
finds that the method based on the extraction of glycerol from the concentrated liquors by means of alcohol and ether is
useless, unless the final evaporation is conducted in a vacuum, owing to the loss of glycerol by volatilisation. The lead
oxide process gives good results with glycerols of fair purity, but in samples containing notable quantities of free alkali,
sulphates, or resinous substances, the method gives untrustworthy results. The dichromate method is rapid, accurate,
and presents no difficulty. With pure glycerol the oxidation is absolutely quantitative. Crude glycerols are treated as
follows:--For the removal of chlorine and of aldehydic compounds, some silver oxide is added to a weighed quantity of
the sample (about 1.5 grams), which is placed in a 100 c.c. flask. After slight dilution, the sample is allowed to remain
with the silver oxide for about 10 minutes. Basic lead acetate is then added in slight excess, the bulk of the mixture
made up to 100 c.c. and a portion filtered through a dry filter. 25 c.c. is placed in a beaker, and treated with 40-50 c.c. of
standard dichromate solution and about 15 c.c. of strong sulphuric acid; the beaker is then covered with a watch-glass,
and heated for two hours in boiling water. After this, the excess of dichromate is titrated back with ferrous ammonium
sulphate. The acetin method (Abstr., 1888, 1345) is rapid and simple, and gives concordant results when the following
precautions are observed:--The heating at the various stages should be carried on in a reflux apparatus, and the sodium
acetate should be cautiously heated before use. After acetylation is complete, the operations should be conducted as
rapidly as possible, owing to the fact that triacetin is gradually decomposed when in contact with water. The free acetic
acid must be neutralised as cautiously as possible, and with rapid agitation of the diluted solution, so that the alkali may
not be locally in excess more than is unavoidable, on account of its action on the triacetin. To ensure the greatest
amount of accuracy, the author advises taking the mean of the results obtained by the dichromate and triacetin methods.
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3. Analysis of butter
By Bondzynski, S.; Rufi, H.
From Zeitschrift fuer Analytische Chemie29, 1-6. Language: Unavailable, Database: CAPLUS
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The most characteristic constituents of butter are the volatile fatty acids, or rather their glycerides. Since the same acids
are also freely soluble in water, the separation of them by distillation can be replaced by one of the following more
convenient methods:--(1.) 4-5 grams of the butter is saponified with 50-60 c.c. of N/2 alcoholic potash, and the
unneutralised potash is titrated by N/2 hydrochloric acid. The alcohol is then evaporated off, and the soap is
decomposed by an excess of hydrochloric acid. The precipitated, insoluble fatty acids are washed with hot water on a
filter, dissolved in alcohol, and titrated with N/2 or N/4 potash. The difference between the quantity of potash neutralised
in the saponification and that required by the insoluble acids gives the amount corresponding with the volatile acids. (2.)
4-5 grams of the butter is saponified; the alcohol is removed by evaporation, and the aqueous solution is treated with the
exact amount of hydrochloric acid necessary for neutralising the potash used. The insoluble fatty acids are washed, and
the soluble acids in the filtrate are titrated with N/10 potash. The results of these methods agree with one another, and
with the distillation process. The insoluble acids can be dissolved in ether, and weighed after evaporation. If then titrated
with potash, the corresponding amount of glycerol can be calculated, and therefrom that of the glycerides of the insoluble
acids, which by difference gives the amount of the glycerides of the volatile acids. Fresh butter always contains small
quantities of free insoluble acids and oleic acid; free volatile acids are not present. As the butter becomes rancid, the
increase in acidity is due mainly to the insoluble acids. Free volatile acids are only developed at a somewhat advanced
stage of rancidity. The free acids can be estimated by dissolving about 20 grams of the butter in alcohol and ether, and
titrating with N/20 alcoholic potash. Or an ethereal solution may be treated with dry calcium hydroxide, when the calcium
salts of palmitic, stearic, and other related acids form a precipitate, which can be collected, decomposed by sulphuric
acid, and extracted with ether. The calcium oleate remains in solution. If the solution is evaporated and burnt, and the
lime weighed, the oleic acid can be calculated from it. Free volatile acids can be estimated by melting the butter in hot
water, washing on a filter, and titrating the filtrate. Phenolphthalein should in all cases be used as indicator. Some
experiments have also been made towards the estimation of hydroxy-acids in butter by Benedikt's acetylation method
(Abstr., 1887, 620). The acetyl number 18.2 was found for butter.
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4. Investigations over the secretions. [machine translation]

By Tschirch, A.; Germann, H.
From Arch. der Pharm. (1896), 234, 641-47. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. 22. Over the fruits of Myroxylone Pereirae and the white Peru balsam. That so-
called "white Peru balsam" is obtained by pressing the fruits out by Myroxylon Pereirae. In order to study its composition,
some Kilogram of these fruits, seeds and fruit bowls were separated, examined. A. The seeds: The same contained 1%
Cumarine crystal at their surface about. The fat of the seeds consists of glycerin esters of the stearine, palmitine and
oleic acid. B. The cases: The same were extracted roughly powdered with hot alcohol. When cooling off a wax-like
compound separated, which dried a reddish, with 95° melting powder formed and Myroxocerine, C12H20O, was called.
The filtered off alcoholic excerpt gave arrears after evaporation, from which with hot water Fe-becoming green tannin and
glucose (the tannin forms Phlobaphene at air) could be obtained. Those into hot water insoluble resinous components
left themselves through one percent KOH in one potash soluble and one potash insoluble divided part. Potash soluble
resin could be separated by concentrated KOH nearly completely again and gave to boiling petroleum ethers one in
white lamellas crystallized compounds, which Myroxofluorin, C42H64O10, off, which give with concentrated H2SO4 a red-
yellow, strongly fluorescent solution. Furthermore contained potash soluble resin a acetylatable alcoholic substance, the
Myroxol, C46H68O10. In one percent caustic potash solution insoluble part consists of Myroxoresen, C7H10O, which with
concentrated HNO3 picric acid forms. The cases extracted with alcohol gave a yellow, brittle resin, which by treatment
with hot acetone (where insoluble) with ether into a white, odorless in alkalis insoluble powders, which ignored Myroxine,
C23H36O. The cases contained neither Cumarine, nor cinnamic acid, of Benzoic acid, Vanillin, "Myroxocarpine" (found
by Stenhouse alleged) or "Myroxylin". The fruits of Myroxylon by contained after available investigation no components
occurring in the usual Peru balsam.
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5. To the Glycerin determination in the wine. [machine translation]

By Boettinger, Karl
From Chem.-Ztg. (1897), 21, 658-59. Language: Unavailable, Database: CAPLUS
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[Machine Translation of Descriptors]. The procedure used by the author exists in the transformation of the Glycerins into
its aceto compound after by the author (Liebig'S Ann. 263. 359) described procedures using potassium bisulfate, which
are obtained by draining acid potassium sulfate and acetic acid anhydride. Execution: Into a small flask with far neck of
about 10 g weight and 7.5 ccm capacity, provided with ground in glass plug, 1 g Bisulfate is weighed sharply, whereupon
the substance on the Bisulfate, which can be examined, is trickled off and weighed again. One adds 1-1.5 ccm acetic
acid anhydride on that, locks the piston, vibrates contents carefully in disorder and heats 2 hours in the landing on water
skirt cabinet. At expiration of this time acetylating is terminated. One shifts the product first also a few drops absolute
alcohol, then waits for some minutes, gives several cubic centimeters ethers in addition and is well-agitated. The ethers
solution by a small filter is poured, the salt repeated with ether is completed and the cut off edge of the filter in the filter is
washed last. Ether the filtrate, 25-30 ccm, is collected in the tared beaker, evaporates and then dried for 4 hours long
with exactly 105°. A yellow oil remains behind, insoluble in water. Managing procedure applied authors on the so-called
analytic wine glycerin and to excerpt used for its production, which had been isolated in well-known way from lime
washed 1896 white wine. In a first test series it resulted that on the average entire alcoholic from 12 experiments 48.3%
of the excerpt remained soluble in the alcohol-ether mixture and as so-called wine glycerin have to be responded.
Extract was acetylated now. On the average 100 extract resulted in 92.7 aceto compound. Whereupon that was
acetylated so-called wine glycerin. 100 parts of the latter produced on the average 134.4 parts of aceto compound, while
100 parts produce pure glycerins of 237 parts of aceto compound. Under the condition that the reaction ran
quantitatively, it does not compute in the so-called wine glycerin 43.3% acetylatable or volatile substance. It was shown
however that available, by heating up on 170° drained glycerin only in the relationship 100 : 151.4 trimonacetin, thus also
not the theoretical quantity produces, although with more than so-called wine glycerin. Finite resulted that 100 parts of
the dry wine extract produce on the average 51.3 parts trimonacetin.
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6. The Caffeine compound in the cola nut: Part II. Colatannin. [machine translation]
By Knox, James W. T.; Frescott, Albert B.
From Journ. Americ. chem. Soc. (1898), 20, 34-78. Language: Unavailable, Database: CAPLUS
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[Machine Translation of Descriptors]. Authors concern themselves with the question whether the tannin of them in former
times (Journ. Americ. Chem. Soc. 19. 63; C. 97. I. 931) discovered cola tannates to in the cola nut occurring free tannin
is identical, since the results of analysis received at that time seemed to speak for a difference of both compounds. First
the authors give a composition of the newer literature about the tannin to the oak, with which the colatannin in its whole
behavior at most agrees. The results of the own investigation are the subsequent: "Free" colatannin. In former times
indicated the method to pure preparation of the preparation is replaced now by a better. The fresh cola nut is in-cut into
boiling alcohol and removed after some instants again and dried in a warm air flow. The pulverized drug is then
extracted using the before used alcohol, with 50% alcohol and extract in vacuum with 18-20° releases from the alcohol.
The residue is filtered, is the undissolved caffeine colatannate. The remainder of this compound is precipitated from the
filtrate with common salt and filtered off again. The filtrate is vibrated out of the chloroform with a little ether, dissolved
from alkaloids and fat with chloroform, then to the removal, first to the removal and finally with acetic-ether, what the
latter tannin takes up. That acetic-ether becomes under decreased pressure distilled off. The residue is only dissolved
in concentrated salt solution and then several times in cold water, vibrated out again and again with acetic-ether,
released finally by a little ether from the last traces of the acetic ether and in the vacuum exicator or also dried with 60-
65°. The received tannin in such a way is a milk colored powder, easily soluble in water, alcohol, acetone, acetic-ether,
little soluble in ether, insoluble in chloroform, and petroleum-ether. The burning resulted in the formula C16H20O8. The
subsequent compilation shows the most important reactions of this tannin and at the same time its agreement with the
calibrated tannic acid, and the difference of the Gallmallic tartaric cid. Free colatannin, Colatannin from caffeine
compound, Calibrated tannin, Gallmallic tannin; Iron acetate, green, green, green, blue-black; Potassium dichromate,
dark-brown precipitation, dark-brown precipitation, brown precipitation, brown precipitation; Chlorine, bright precipitation,
bright precipitation, -, -; Bromine, light-yellow precipitation, light-yellow precipitation, yellow precipitation, no precipitation;
Ca(OH)2, pink, then red, finally precipitation, pink, then red, finally precipitation, red, finally precipitation, dark-blue, then
precipitation; Tartar emetic., no precipitation, no precipitation, white precipitation, white precipitation; Quinine,
Cinchonin, Caffeine, white precipitation, white precipitation, precipitation, white precipitation; Albumin, precipitation,
precipitation, precipitation, precipitation; Lead acetate, white precipitation, white precipitation, white precipitation, white
precipitation; Red prussiate of potash and ammonia, light red, light red, -, light red; Formaldehyde + HCl, pink
precipitation, then red, pink precipitation, then red, -, -. To the enlightenment of the constitution the subsequent
derivatives of the colatannins were prepared: Pentacetyl colatannin, C16H15(C2H3O)5O8. By one-hour boiling with acetyl
chloride and the casting in of the solution in ice-cold water of white or grey-white powder, insoluble in water, little soluble
in ether, easily soluble in chloroform, alcohol and glacial acetic acid. The entrance was still particularly proven by
saponification of this compound and determination of acetic acid by five acetyl groups. Tribromo colatannin,
C16H17Br3O8. By addition from excess bromine water to aqueous tannin solution of light brown-yellow, voluminous
precipitation, which becomes red-brown with drying. Insoluble in water, ether, chloroform, benzene, easily soluble in
alcohol and acetone. Pentacetyltribromocolatannin, C16H12Br3(C2H3O)5O8. By boiling the bromine compound with
acetyl chloride or by addition of a excess from bromine to the chloroform solution of the acetyl compound gold-yellow
powder, insoluble in water, very little soluble in ether, soluble in alcohol, acetone and chloroform Tetrabromocolatannin,
C16H16Br4O8. By addition from excess bromine to alcoholic solution of the tannin and casting in the solution into the
fifteen times the quantity of water. Somewhat darker than the tribromine compound, of similar solubility.
Pentacetyltetrabromocolatannin, C16H11Br4(C2H3O)5O8. Of similar characteristics as the tribromine compound.
Pentabromocolatannin, C16H15Br5O8. Formed during the preparation of the hexadecimal bromine compound, when the
added bromine quantity was not sufficient, however perhaps is a mixture of Tetra- and hexabromine compound. Of
similar solubility, but more darkly and less steady, than the other bromine compounds Pentacetylpentabromocolatannin,
C16H10Br5.(C2H3O)5O8. By acetylation of the previous compound or by bromination of the acetyl compound into
alcoholic solution with an excess of bromine, whereby not as was expected, a hexadecimal bromine compound develops.
Hexabromocolatannin, C16H14Br6O8 resembles the other acetyl bromine compounds. By addition of a large excess from
bromine to alcoholic tannin solution. Darker than the other bromine compound, but of same solubility.
Tetracetylhexabromocolatannin, C16H10Br6(C2H3O)4O8. By acetylation of the hexadecimal bromine compound dark
yellow, soluble in chloroform and alcohol, insoluble in water. Anhydrides. First colatannin anhydride, (C16H19O7)2O. By
heating the tannin up on 107-110°, yellow-red, soluble in water, alcohol and diluted alkali. First Tribromocolatannin
anhydride, (C16H16Br3O7)2O. By bromination of the previous compound into aqueous solution first Tetrabromocolatannin
anhydride, (C16H15Br4O7)2O. Developed in the same way like the appropriate Tannin derivative First
Hexabromocolatannin anhydride, (C16H13Br6O7)2O. Analogous one prepares. Dark-red, insoluble in water, ether and
chloroform soluble in alcohol and diluted Alkali third colatannin anhydride, (C16H17O6)2O. By heating the tannin up on
135-140°, reddish-brown powder, insoluble in water, ether, chloroform, soluble in alcohol and alkali. Third
Tetrabromocolatannin anhydride, (C16H13Br4O6)2O. Dark-brown, insoluble in water, ether and chloroform, soluble in
alcohol and alkali. Third Hexabromocolatannin anhydride, (C16H11Br6O6)2O. Dark brown one, of same solubility. Fourth
colatannin anhydride, C16H16O6. By two-hours heating of the tannin up on 155-160°. Of same characteristics. Fourth
Tetrabromocolatannin anhydride, C16H12Br4O6. Of same characteristics. Fourth Hexabromocolatannin anhydride,
C16H10Br6O6. Very-dark-brown, of same solubility. When boiling the colatannins with diluted acid a red compound
(Knebel's cola red) develops, from intermittent composition beside Protocatechuic acid. When melting with potash
hydrate phloroglucinol and Protocatechuic acid develop. Latter acid develops also with heating up with glycerol on 200°.
From the caffeine colatannate isolated tannin proved as perfectly identical to foregoing described compound and resulted
in the same derivatives. The colatannin is not after the investigations of the authors glucoside, and the alleged glucose
formation from the same is to be led back to incomplete removal of the glucose originally existing in the plant. After the
present results the authors strike the formula for the colatannin: C6H3(CH3)(OH)3-CO.O-C6H3(CH3)(OCH3)(OH)2
forwards and subjected finally still the newer research methods about this object of a critical view.
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7. Over the acylation of the alcohols and phenols in pyridine solution. [machine translation]
By Einhorn, Alfred; Hollandt, Friedrich
From Liebig's Ann. (1898), 301, 95-115. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. (Reported by Alfred Einhorn). The acylation of the alcohols and phenols in
pyridine solution runs smoothly and supplies frequently different products than the method of Scot Baumann. Particularly
with multi-valued alcohol, phenols and their carbonic acid it leads frequently too partially acylated compounds, before all
also with alkali-sensitive multi-valued phenols. One can do also in acid solution(glacial acetic acid) acylate, obtains
however with benzoyl chloride in glacial acetic acid solution by pyridine the quantitative acetyl compound; a reaction, the
authors by one already in the cold running conversion of the primarily developing Benzoyl pyridine chlorides with glacial
acetic acid to Acetyl pyridine chloride and Benzoic acid explain: C5H5N.(Cl)CO.C6H5 + CH3.CO2H = C5H5N(Cl).CO.CH3
+ C6H5CO2H. Taken place via the Acetyl pyridine chloride, as was proven, then the acetylation. The method is
extended by application of acid hydrate and phosgene (see Kempf, J. pr. Chem. [2] 1. 414), which already give acid
chloride with presence of pyridine at usual temperature and cause an acylation. Experimental. Alcohols or phenols are
dissolved into 3-5 parts pyridine and the acid chloride under cooling is in addition-given; after 3-5 hours into cold diluted
sulfuric acid one introduces in drops. From glycerol and benzoyl chloride: Tribenzoyl glycerin, C3H5(OCO.C6H5)3,
melting point 76°. Erythritol with 4 moles benzoyl chloride supplies the, trichloroethylene and Tetrabenzoyl erythrite;
separation by ether, in which the tri compound is most easily, the compound more heavily and the Tetra compound
soluble not at all. Dibenzoyl erythrite, C4H6(OH)2(OCO.C6H5)2, small needles from alcohol benzene; melting point 154-
157°, easily soluble in glacial acetic acid. Tribenzoyl erythrite, C4H6(OH)(OCO.C6H5). Small needles from alcohol;
melting point 108-110°. From mannitol Dibenzoyl mannite, C6H8(OH)4(O.CO.C6H5)2; develops for in the heat star-
shaped needles grouped; melting point 178°; little soluble in glacial acetic acid, insoluble in ether, benzene, chloroform.
The acylation of the phenols runs according to the method quantitative, sometimes even with fewer pyridines.
Implemented at eugenol, i-eugenol, β-Naphtol pyrocatechol supplies Monobenzoylpyrocatechin (small needles, melting
point 134°) beside Dibenzoylpyrocatechin(cubic-shaped crystal; melting point 88°). From resorcinol the
Monobenzoate(small lamellas from alcohol develops; melting point 135-136°) only in small quantity, mainly the
Dibenzoate, melting point 117°. Pyrogallol is converted into mono and Tribenzoyl compound; separation by soda lye.
Monobenzoyl pyrogallol, C6H3(OH)2(O.CO.C6H5). Prisms from chloroform or glacial acetic acid; melting point 140°;
easily soluble in ether, alcohol, insoluble in water. Tribenzoyl pyrogallol, C6H3(OCO.C6H5)3; small prisms from alcohol;
melting point 89°. Dibenzoyl pyrogallol, C6H3(OH)(OCO.C6H5)2, formation without pyridine by 2 moles benzoyl chloride
on the water bath. Solidified slowly microscopic needles from toluene; melting point 100°; easily soluble in ether,
chloroform and alcohol, little soluble in benzene, insoluble in water. Give with FeCl3 no color reaction. By acetyl chloride
Triacetyl pyrogallol, melting point 160° always develops with presence of pyridine;. Monoacetyl pyrogallol,
C6H3(OH)2(O.CO.CH3), forms with heating the phenol up with acetyl chloride on the water bath without pyridine. Glossy
needles from water; melting point 171°; easily soluble in alcohol, glacial acetic acid, little soluble in chloroform, very little
soluble in ligroin and benzene; becomes dull brown by FeCl3. Pyrogallol tricarbonic acid ethyl ester, C6H3(O.CO2.C2H5).
From formation the Pyridine method. Small prisms from alcohol; melting point 58-60°; very easily soluble in chloroform,
benzene, soluble in ether, insoluble in water. CO3(C2H5)2 disintegrates to and with distillation into CO2, (equation or
structure in original text). The mono carbonic acid ester was not preparable; in use of fewer chlorine carbonic acid esters
develops beside many trichloroethylene, little Pyrogallol dicarbonic acid ester, C6H3(OH)(O.CO2.C2H5). Separation by
soda lye. Boards from water; melting point 83°; colors itself green with FeCl3. Tribenzoylgallic acid,
C6H2(O.CO.C6H3).CO2H. Formation after the Pyridine method; needles from alcohol, melting point 191-192°.
Tribenzoylgallic acid methyl ester, C6H2(O.CO.C6H5).CO2CH3, forms also when using little benzoyl chloride. Wart-
shaped aggregate; melting point 139°. With p-Amidosalicylic acid ester by acetyl chloride and pyridine first the amido
group is assailed: acetyl p-amidosalicylic acid methyl ester, CH3.CO.NH4.C6H3.(OH)2.CO1 2.CH3; Needles from alcohol;
melting point 147°; soluble in diluted soda lye. The acylation of the phenols by benzoyl chloride in glacial acetic acid
pyridine solution takes place smoothly in the cold; one can instead of C6H5.COCl also another acid chloride(Phthalyl
chloride) use and always receive with presence of glacial acetic acid the acetyl compound. The acylation of the phenols
with acid and phosgene runs in pyridine solution in the cold. In the case of use other one obtained to acid instead of
glacial acetic acid: Propionyl β-Naphthol, C10H7.O.CO.C2H5; needles from alcohol; melting point 51°; smells anise-like. i-
butyryl-β-Naphthol, C10H7O.CO.C3H5; needles from alcohol by water; melting point 43°; smells in the heat aromatically.
i-Valeryl-β-naphthol, C10H7.O.CO.C4H9. Colorless, rancid smelling oil; solidified in the refrigerant mixture to needles;
b.p.20, 180-184°. The formylation of the phenols with formic acid, pyridine and phosgene succeeded only with the
Eugenolene; with the others the carbonates developed. Formyleugenol, C10H12O3; formation in the refrigerant mixture
colorless liquid, smells like eugenols: b.p.20, 150°; soluble in alcohol, insoluble in water and soda lye. Formyl-i-eugenol,
C10H12O3 b.p.20, 155-160°; the normal compound very similar. Both do not supply hydrazone with phenylhydrazine, but
it develops for Formylphenylhydrazide: C6H5(C3H5)(OCH3).OCHO + C6H5N2H3 = C6H3(C3H5)(OCH3).OH +
C6H5NH.NH.COH. o-creosol carbonate, [C6H4(CH3)O]2. CO; silk-glossy needles from alcohol; melting point 60°; easily
soluble in glacial acetic acid, chloroform, benzene. β-Naphthol carbonate, (C10H7O)2CO; satin-glossy lamellas from
toluene; melting point 178°; soluble in benzene, very little soluble in alcohol, nearly insoluble in ethane.
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8. About the tribasic alcohol from Allyldipropylcarbinol. [machine translation]

By Bogorodsky, Alexis
From Journal fuer Praktische Chemie (Leipzig) (1898), 57(2), 35-38. Language: Unavailable, Database: CAPLUS
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[Machine Translation of Descriptors]. From oxidation of Allyldipropylcarbinol with KMnO4 in 1% aqueous solution a
glycerol results to, C10H19(OH)3 = (C3H7)2.C(OH).CH2.CH(OH).CH2.OH. With difficulty mobile, colorless syrup; easily
soluble in alcohol and water. With experiments, to acetylate it, in each case a mixture of the triacetate developed,
C10H19(O.CO.CH3)3 and a Diacetates, Cl0H18(O.COCH3)2, which forms from the unsaturated bivalent alcohol, which
results from the glycerol from water cleavage.
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9. The theory of saponification. [machine translation]

By Lewkowitsch, J.
From Journal of the Chemical Society (1899), 15, 190. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. Authors shows that over the saponify theory, according to which the hydrolysis of
the triglycerides is accepted as a tetramolecular reaction it will leave the opinion must to favors of the Geitel's theory,
which regards the reaction as more bi-molecular. If this is like that, then the diglycerides would have and monoglycerides
in partly which saponified fats to occur. Author proves its present by acetylation of the intermediate products, which are
released from glycerol, and shows that the acetylating products show substantial acetyl values, which rise and fall with
the innovation of the saponification. For the confirmation also the quantities the insoluble fatty acid in the acetyl products
were intended and likewise the Saponification values. The curves obtained with both test series agree satisfactory.
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10. Treatment of the p-Nitranilines on triiodine and Tetraiodobenzol, on the Pentaiodobenzol, as well as on all
intermediates leading to these compounds. [machine translation]
By Willgerodt, C.; Arnold, Emil
From Berichte der Deutschen Chemischen Gesellschaft (1901), 34, 3343-54. Language: Unavailable, Database:
CAPLUS
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[Machine Translation of Descriptors]. By introducing vaporous chlorine iodine in hydrochloric acid, or Chloroform
solutions of the p-Nitranilines have MICHAEL and NORTON (Ber. Dtsch. Chem. Ges. 11. 113) already the 2-Iodo and
2.6-Diiodo-4-nitroaniline represented; better is, however, the following method. Preparation of 2-Iodo-4-nitroanilin, NO2.
C6H3I. NH2. One lets a glacial acetic acid solution of 11.77 g chlorine iodine flow into a coldly saturated solution of 10 g
p-Nitraniline into glacial acetic acid under agitating into glacial acetic acid, casts in after short time in 1 liter boiling water,
boils up and filters. Yellow needles; melting point 105°. The 2.6-Diiodo-4-nitroaniline developing with this reaction only
in small quantities, NO2. C6H2I2. NH2, forms in plentiful measure, if one 50 g p-Nitraniline in 300 ccm 60-80° warm glacial
acetic acid soluble and to this liquid 115 g chlorine iodine, dissolved in 200 ccm about 50° warm glacial acetic acid under
constant agitating adds, after which expiration of the first, rather lively reaction still 2 hours warms up, then in 3 liters
boiling water casts in and by introducing steam about free iodine become, as well as the largest part of the salt and
acetic acid drives off. Citron-yellow needles from acetic ester; melting point 243-244°. By gradual causing of 10-12 g
firm sodium nitrate to a solution of 30 g 2.6-Diiodo-4-nitroanilin in 50 ccm of concentrated sulfuric acid with 5°, in to two-
hours execution of the mass and slow registering the same alcohol boiling in 250 ccm developed for 3.5-
Diiodonitrobenzol, C6H3I2. NO2. Yellow needles from alcohol; melting point 95-96°; well soluble in ether, alcohol,
chloroform, hot glacial acetic acid, benzene; volatile with steam. The reduction of the 3.5-Diiodonitrobenzols with SnCl2
into alcoholic salt-acid solution gave 3.5-Diiodoaniline, to C6H3I2. NH2; transparent, light-sensitive needles from alcohol;
melting point 105°; the salts are not divided with boiling water. Sulfate. Glossy, light sensitive lamellas from diluted
sulfuric acid; decomposing itself above 200° under separation of iodine. Chlorine hydrate; light sensitive needles from
hydrochloric acid; decomposing itself above 200°. Platinum salt, C12H12N2Cl6I2Pt. Yellow needles with acetyl
compound, C8H3I2 (NH. COCH3), through five to six-hours cooking of the base with glacial acetic acid represented;
needles; melting point 101-102°; soluble in glacial acetic acid, alcohol, ether. 1.3.5-Triiodobenzol, C6H3I3, developed,
when a cooled with ice solution of 10 g 3.5-Diiodoanilin shifts concentrated hydrochloric acid with 3 g sodium nitrate in 50
ccm gradually, the developed diazo solution still 1 hour agitated, mixed with 8 g KI in 20 ccm ice water and gradually on
50° warmed up. Flexible, white needles from glacial acetic acid; melting point 180°; sublimatable; volatile with steam;
rather few soluble in ether, chloroform, CS2, benzene, cold alcohol, more easily into boiling glacial acetic acid. On similar
way with concentrated hydrochloric acid combined with 2.6-Diiodo-4-nitranilin became diazotized and the effect of KI to
the 3.4.5-Triiodonitrobenzol, C6H2I3. with concentrated hydrochloric acid; NO2, receive; yellow needles from alcohol;
melting point 105°; easily soluble in alcohol, ether, chloroform, benzene, hot glacial acetic acid; sublimatable; volatile with
steam. The reduction of this compound to the 3.4.5-Triiodoanilin, C6H2I3. NH2, carries out itself, if one adds a hot
alcoholic solution of 50 g the same gradually hot hydrochloric acid to a solution of 70 g Sn-Chloride in 150 ccm
concentrated hot hydrochloric acid. White, extremely light sensitive needles from ethers; melting point 78°; easily soluble
in alcohol, ether; volatile with steam. The alcoholic solutions of the base through concentrated acid of precipitable salts
decomposing themselves when heating up, keeping, as well as cooking, with water. Sulfate. Lamella. Chlorine hydrate.
Needles. Platinum salt, C12H10N2Cl6I6Pt. Reddish needles. Acetyl compound. Needles from alcohol; melting point
135°. SKRAUP's synthesis changes the 3.5-Diiodoanilin in m-ana-Diiodoquinoline (I.); (sublimatable needles from
alcohol; melting point 132°; the salts crystallizes from diluted acid; Chlorine and Iodomethylate melting above 250° under
decomposition) and the 3.4.5-Triiodoaniline in m-p-ana-Triiodoquinoline (II.); (needles from alcohol; melting point 102°)
over; the 2.6-Diiodo-1.4-phenylendiamine decomposes during the effect of glycerol of sulfuric acid, (see original
document for graphics). The 3.4.5-Triiodoaniline becomes of concentrated sulfuric acid decomposing, lets themselves
however in a mixture from same parts of these acid and absolved alcohol diazotize; with at the most 5° received diazo
solution gave 1.2.3-Triiodobenzol, C6H3I3 with the pan boiling with alcohol. White, light-sensitive needles from alcohol
water; melting point 86°; sublimatable; very easily soluble in alcohol, ether, chloroform. With KI diazotize width units
3.4.5-Triiodoaniline under formation of 1.2.3.5-Tetraiodobenzol, C6H2I4 reacted. Crystals from glacial acetic acid or
ether; melting point 148°; sublimatable; few soluble in alcohol, ether, chloroform; easily soluble in boiling glacial acetic
acid. By warming up 2.6-Diiodo-4-nitroaniline with SnCl2 HCl 2.6-Diiodo-1.4-phenylendiamin, C6H2I2 (NH2)2; one
received white, very light-sensitive needles from water; melting point 108°; easily soluble in alcohol, ether; acetylate did
not leave itself with glacial acetic acid; supplied no salts; becomes of chromic acid 2.6-Diiodoquinone, C2H2I2 (: O) 21,4,
oxidizes. Gold-glossy lamellas; melting point 178°. Chlorine iodine converts the 2.6-Diiodo-p-phenylendiamin into warm
glacial acetic acid into 2.3.5.6-Tetraiodo-1.4-phenylendiamin, C6I4 (NH2) 2; extremity light sensitive crystals from ether
alcohol, against 152° melting; very few soluble into hot water; easily soluble in alcohol, ether. C6H2I4 gave with the
Entamidieren 1.2.4.5-Tetraiodobenzol; white, sublimatable needles from ethers; melting point 165°; few soluble in
alcohol, ether; somewhat light-sensitive. By causing 7 g chlorine iodine, dissolved in 20 ccm glacial acetic acid, to a
cooled solution from 20 g 3.4.5-Triiodoaniline in 100 ccm concentrated hydrochloric acid forms, C6HI4. for 2.3.4.5-
Tetraiodoaniline; NH2; needles from alcohol; melting point 92°; easily soluble in alcohol, ether; colors itself soon violet at
the light. The base was transferred by Entamidieren in 1.2.3.4-Tetraiodobenzol, C8H2I4; sublimatable, in alcohol, ether,
chloroform easily soluble crystals of the melting point 114°. Of the three Tetraiodobenzol of the authors (melting point
148°, 165°, 114°) none is correct in the melting point with the two Tetraiodobenzol ISTRATI's (melting point 220°, 247°),
during like known in this case only three isomers possible are. The diazo compound of the 2.3.4.5-Tetraiodoaniline
converted itself with KI under formation of Pentaiodobenzol, C6HI5; white needles from alcohol; melting point 172°;
sublimatable; few soluble into cold alcohol, ether; more easily soluble in chloroform, hot glacial acetic acid.
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11. Procedure for preparation of incompletely acetylated Polyhydroxyl compound. [machine translation]
From Ger. Offen. (1901), DE 122145 19010505, Language: German, Database: CAPLUS
SciFinder® Page 8
[Machine Translation of Descriptors]. If one heats the para-acetyl compound up with the unmodified output bodies in the
calculated quantitative proportions, easily available by direct acetylation, then the acetyl groups distribute themselves
about the total amount of the existing acetylate hydroxyls. From same parts glycerol and tri mono acetine develop with
200° Mono acetine, Kp16.5, 158°. From resorcinol and Resorcine diacetate one receives by heating up on 170° an oil not
solidifying with the cool one, resorcine mono acetate. Heats up one same parts pyrogallol and Pyrogallol triacetate or 2
parts Pyrogallol with 3 parts Pyrogallol diacetate on 160°, then pure Pyrogallol mono acetate, soluble in water, Kp25
develops about 185°. Anthrapurpurintriacetate gives with Anthrapururine with 200° Anthrapurpurindiacetate, melting
point about 175° (from glacial acetic acid crystallizer).
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12. Over the effect of sulfuric acid on the glycerol from Allylmethyltertiarybutylcarbinol. [machine translation]
By Petschnikow, A.
From Zhurnal Russkago Fiziko-Khimicheskago Obshchestva (1901), 32, 780-94. Language: Unavailable, Database:
CAPLUS
[Machine Translation of Descriptors]. During the effect of diluted H2SO4 on the compound mentioned (on 5 g of the
glycerol 250 g water and 5 g 50% H2SO4) was received in water insoluble oils and a liquid soluble in water and ether.
When using not completely pure glycerol still another firm body resulted. Liquid, water-soluble product, C9H18O2, has a
Kp751, 214-215°, D204, 0.96998 and P (na -1 / d) = 73.66. It results from the raw material from extraction of a molecule
water; one of the two following formulas comes to it: (see original document for formulas). At present does not let itself
decide yet, which of the two formula pictures is the true. Author came to the list the same due to the subsequent
experiments. The product gives with heating up with acetic anhydride in the course melted pipe (3 days on 100°) a mono
acetyl product, C9H17OC2H3O; through this it is proven that in the examined compound only one hydroxyl group is
present. The optical investigation points on the fact that no double bond is present. An alkaline copper solution or
ammoniacal AgNO3 is not reduced. To the compound thus neither aldehyde, nor Ketone character come. With heating
up with water or aqueous H2SO4 on 150° no hydration occurs, which also to favor one γ-Oxides speaks. During the
foregoing experiments on the Formula I. point, speak the oxidation with chromic acid mixture for second. One receives
namely here γ-Lactone, of the melting point 96-98°, as beautiful tablet; easily soluble in alcohol and ether, little soluble in
water. The Lactone is identical to the crystalline compound, which was initially described and with the distillation of the
impure glycerol from Allylmethyltertiarybutylcarbinol with H2SO4 develops. The Lactone forms here at expense of β-
Methyltertiarybutylethylene lactic acid, which is mixed to the impure glycerol. To the proof of the saying distilled author β-
Methyltertiarybutylethylene lactic acid with H2SO4 under conditions stated for the glycerol and receives likewise the
Lactone from the melting point 96-98°. Barium (C8H15O3) 2, the same one wins the barium salt from the pure compound
and Ba(OH)2 into hot aqueous solution; transparent crystals decompose lichen with heating up. Ca (C3H15O3) 2, from
the Lactone and lime milk represented; amorphous mass. The oily product unsolvable in water, which is won as by-
product during the effect of H2SO4 on the glycerol from Allylmethyltertiarybutylcarbinol, has a boiling point about 210°
and corresponds to the formula C18H34O3 + C18H36O4. It gives with heating up with acetic anhydride on 100° an ester
C18H34O2 (OC2H3O) 2 + C18H34O3. Becomes the oil first with water on 170° heated up and then acetylates, then one
receives the ester C18H34O2 (OC2H3O)2. When oxidizing one receives described the above to oily product with chromic
acid mixture β-Lactone.
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13. About the Allylmethylphenylcarbinol. [machine translation]

By Arbusow, Alexander
From Zhurnal Russkago Fiziko-Khimicheskago Obshchestva (1901), 33, 38-45. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 9
[Machine Translation of Descriptors]. To the examination of the suitability of M. and A. SAYTZEFF's method (LIEBIG's
Ann. 185. 157) the author undertook the preparation of unsaturated alcohols, which belong to the row CnH2n-7, the
production of the Allylmethylphenylcarbinols, C3H5. C (OH) (CH3) . C6H5. To several futile experiments came he to the
subsequent function: Equimolecular quantities of acetophenone and allyl iodide become on zinc splinters, with absolute
ether poured or dripped. After some days becomes the reaction mass water given and in the damp current distilled off.
One the dry received oil with K2CO3 or BaO and subjects it to fractional distillation. The Allylmethylphenylcarbinol is a
easy-mobile liquid of the Kp745.5, 217-223°; D2020, 0.99934; D2020, 1.00040. Yield on the average 31.5% of the theory.
The oxidation of the carbinol to the appropriate glycerol was made by means of a l% aqueous solution of KMnO4 (on 1
mole carbinol and 1 of the atom oxygen). The glycerol, CH3 (C2H5) . C (OH) . CH2. CH (OH) . CH2 (OH), was separated
from the mineral components by extraction with ether. Insoluble water, is alcohol, ether easily soluble syrup. With the
acetylate of the compound with acetic anhydride receives a mixture of the trichloroethylene and Diacetylesters with an
addition of the Diacetylesters of an unsaturated glycol. Oxidation of the carbinol too β-Methylphenylethylene lactic acid.
One uses for this 4% a solution of KMnO4 (on 1 mole Carbinol of 4 atoms oxygen). The filtrates of the manganous
oxides nearly to dry ones are evaporated; the residue is extracted to the removal of the glycerol with ether, also formed.
One acidifies on that with H2SO4 and extracts from the solution free acid with ether. One receives the calcium salt from
the raw acid and CaCO3; (C10H11O3)2Ca. AgC10H11O3; from the acid and AgCO3; wart-shaped aggregate. Zinc
(C10H11O3) 2 + 2H2O; small crystal needles, from the acid and zinc carbonate represented. The free acid from the silver
salt cleaned by crystallization; to star shaped aggregate needles of the melting point grouped 50-53°.
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14. About the Allylmethylbutylcarbinole with normal and secondary butyl. [machine translation]
By Taliew, Konstantin
From Russian Journal of Phys.-Chem. Ges. (1901), 33, 26-35. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. First of these compounds is by effect of finely roughened zinc on a mixture by
Methylnormalbutylketone and allyl iodide. One divides and subjects the received product with water the whole to
distillation. The oil in the presentation is separated, hard cured after the aqueous liquid (with K2CO3) and fractional
distilled. The Allylmethylnormalbutylcarbinole, C9H13O, has a Kp744.7, 176-178°; D200, 0.84412, D2020, 0.84497; the
determination of the refraction ability points to a double bond. The yield amounts to about 24%. The acetic acid ester of
the Allylmethylnormalbutylcarbinols, C9H17OCH3O, becomes from the alcohol by heating up with a small surplus of acetic
anhydride in course-melting. Tube with 100°. Boiling point 196-201°. Colorless liquid. The Allylmethyl secondary
butylcarbinol, C9H8O, is received by effect of zinc on a mixture from allyl iodide and Methyl secondary butylketone. The
further treatment reaction product takes place, how described in the first case. The alcohol is a colorless liquid with easy
turpentine smell of the boiling point 173-175°; D2020, 0.85438; D2020, 0.85526. Yield about 9%. The acetic acid ester of
the Allylmethyl secondary butylcarbinols, C9H17OC2H3O, has a boiling point 190-195°. With the oxidation of the alcohols
with KMnO4 the appropriate develop β-Methylbutyl ethylene lactic acid and as by-products the glycerols concerned. 17 g
Allylmethylnormalbutylcarbinol become with 50 g KMnO4 and 12 g Allylmethyl secondary butylcarbinol with 36 g KMnO4
in 3% aqueous solution (on 1 mole alcohol of 4 atoms oxygen) by cooling on. The filtrates of the manganous oxides and
to dry ones are evaporated to neutralized. From the residue with alcohol the glycerol is extracted and added for the
precipitation of the salts ether. This operation is several times repeated slip pure preparation of the glycerols. Both the
glycerol from Allylmethyl normal butyl-carbinol, and the glycerol from Allylmethyl secondary butylcarbinole is a syrup
soluble easily soluble in water and alcohol in ether. With the acetylate of these products probably forms a mixture of tri=
acetyl compounds. The residues received with the extraction of the glycerols with H2SO4 are divided and worked on with
ether. Here wins the free Methylbutylethylene lactic acid. By saturate with CaCO3 releases it from the oxalic acid also
developed. To the complete purification represents the silver salts, crystallized over, decomposing with H2SO4 and
extracts with ether. β-Methy lnormalbuthylethylene lactic acid and β-Methylsecondarybutylethylene lactic acid form a
crystallized close syrup. The calcium salts, (C8H15O3) 2Ca, both acid are received by saturate the same with CaCO3.
Thin membrane. The barium salts, (C8H15O3) 2Ba, are represented in same way; lightly soluble in water and alcohol.
(C6H15O3) 2Zn; soluble in water and alcohol; only the salt of the first acid shows clear crystallization. C8H15O3Ag; the salt
of the first acid is in water more easily soluble and is light resistant than that second.
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15. About nitro compounds of the Anthragallols. [machine translation]

By Bamberger, Max; Boeck, Fritz
From Monatshefte fuer Chemie (1901), 22, 717-31. Language: Unavailable, Database: CAPLUS
SciFinder® Page 10
[Machine Translation of Descriptors]. Report II. The formation in the first article (Monthly Magazines f. Chemistry 18.
283; C. 97. II. 617) described Pseudonitroanthragallols takes place better and without occurrence of by-products, if
Anthragallol is exposed to steams of anhydrous HNO3 (from concentrated HNO3 + concentrated H2SO4 or concentrated
H2SO4 + anhydrous NaNO3) with room temperature the by nitration. Therefore it follows simultaneously that nitrogen
oxides are not necessary for developing this product. The preparation, α-Nitroanthragallols (reaction product of the
Pseudonitroanthragallols with water) succeeds better by crystallization from alcohol-benzene. A mole of crystal benzene
contains a form of low dark-ruby-red columns. The burning must happen with special caution, there α-Nitroanthragallol
contrary to β-Nitroanthragallol with heating up easily nitrogen oxides states. By acetylation α-Nitroanthragallols by
means of acetic anhydride or acetyl chloride a triacetyl derivative received, C14H4O2 (NO2) (OC2H3O) 3. Citron-yellow
needles (from acetic anhydride glacial acetic acid), melting point 233°. During by effect of alcohol and water on
Pseudonitroanthragallol α and β Nitroanthragallol develops, supplies Pseudonitroanthragallol by heating up with higher
alcohols, Propyl alcohol, Butyl alcohol, glycerine, etc. products, which do not show pseudo nature (solubility in water,
violet; in pyridine, steal-gray color). On the other hand, by warming up, it becomes a methyl-alkohol. Solution a light-
yellow crystal cakes from a pseudo character received, which could not be cleaned because of the easy decompose of
the compound. During the effect of concentrated aqueous HCl in the heat the red Pseudonitroanthragallol under gas
generation is crystal alcohol in long, gold-yellow needles crystal compound converted. Charred in capillary tubes, without
melting. The same seems with β-Nitroanthragallol to be identical, however, not chlorine-free is to be received, to HBr
and HI supplies with likewise stable Nitro products with different halogen content. The aqueous haloid acid during the
effect on Pseudonitroanthragallol are partly oxidized, and that freely becoming halogen arranges the formation of
substitution products, which cannot be separated by crystallize from the Nitro products of the main reaction. In binding
the arising halogen by an organic substance author left a concentrated solution of HCl to the intention in absolute alcohol
the pseudo body affect. The compound developing thereby (gold-yellow needles from alcohol, melting point 223°) as
Monochloranthragallol ore Casting, C14H7O5Cl proved (see F. SLAMA, Inaugural Dissertation, Geissen, 1899; C. 99. II.
967). When warming up Pseudonitroanthragallol with anhydrous formic acid α-Nitroanthragallol is received.
Pseudonitroanthragallol gives a steel-blue solution with pyridine. With long standing, with rapid warming up, changes the
color from green to red-brown. This solution contains a Pyridine salt of the Pseudonitroanthragallols, which will form a
solution from pseudonitroanthragallol in water- and water-free- acetone with acetone-pyridingemisch in in indigo blue
crystal goedes by shifting a solution from Pseudonitroanthragallol in water. It develops also directly from
Pseudonitroanthragallol and dry Pyridine vapor at usual temperature. light in water and pyridine, insoluble in alcohol,
ethene benzene. Its composition corresponds to the formula C14H8O5. HNO3. C5H5N. From the existence of this salt
and the ability of the Pseudonitroanthragallols to decompose when warming up into alcoholic or aqueous solution
BaCO3, CaCO3, Na2CO3, Ag2CO3 authors conclude to the presence of a hydroxyl group distinguished by particularly
acid characteristics. With the experiment, this acid hydroxyl group by means of acetyl chloride to acetylate, was received
a chlorine-containing, to a pseudo character compound showing, indecomposable and therefore to be kept completely
pure could not. Red, weak bluish resplendent crystals. Water soluble into the usual solvents with yellow color. The
analysis figures correspond approximately to the formula C10H10O8NCl. With heating up takes place from about 110° at
brown discoloration and cleavage of acetyl chloride. Authors believe that the formation of the Pseudonitroanthragallols
lower entrance of the entire Saltpeter acid molecules takes place, and set up Formula I as probable constitutional
formula, (see original document for graphics). From water separation, the stable Nitro bodies result, and can be
understood as Isonitro bodies ( Formula II.) to α-products, (see original document for graphics).
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16. Quantitative experiments with the fermentative lipolysis. [machine translation]

By Hoyer, E.
From Seifenfabrikant (1903), 23, 1093-96. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. See tungsten. CONNSTEIN, E.HOYER and H.WARTENBERG, Ber. Dtsch. Chem.
Ges. 35. 3988; C. 1903. I. 100. From splitting with palm kernel oil, linseed oil, excrement clay oil, cocos oil, palm oil and
peanut oil that follows the yield of fatty acid from a fat split after the fermentative method is alike to the weight of the
applied fat, as the being added Ricinus oil acid covers the weight decrease by formation of glycerol (8-11% of the oil).
The height of the cleavage varied between 85-93%, and the Glycerine water was 8-12%. The stock of the splitting the
degree of a oil is warmed up in the beginning of taken emulsion sample in a test glass with 4-5 drops of 25% H2SO4,
briefly boiled up and the settling of the fatty acid by hanging up the test glass into a vapor bath or into boiling water is
accelerated. The separated clouded fatty acid into a new test glass is poured off by heating the drained by a small filter
is clearly filtered, 2 g with 60-80 ccm 95% alcohol in Erlenmeyer flasks on a water bath for heating up and with normal
KOH and Phenolphthalein as indicator in titration. 2 g of 100% Fatty acid becomes saturated with Palm kern oil acid by 9
ccm normal KOH; "Cocos oil acid" 9.4 ccm in KOH; "Linoleic acid" 7 ccm in KOH; With excrement of tone oleic acid by
7.4 ccm in KOH; "Peanut oleic acid" 7.2 ccm in KOH; "Palm oil acid" 7.5 ccm in KOH; Stocks of the glycerol of 100 g of
a representative sample of the united Glycerin water of a beginning with the quadruple quantity of absolute alcohol and
the 1 1/2-1/2-fachen quantity of ether transferred and over night stand calmly. Filtered off the separated protein materials
on the filter with fresh alcohol-ether mixture is washed. The alcoholic-ether and Glycerol solution is evaporated in a
weighed glass beaker or piston on the water bath to the disappearance of the smell according to alcohol and determined
in such a way the produced raw glycerin of the actual glycerol content by acetylation.
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SciFinder® Page 11
17. Over Glycerine Determination With Special Consideration of the Applicability of the Extraction Method on the
Fermentative Glycerine Water. [machine translation]
By Landsberger, W.
From Chem. Rev. Fett- u. Harz-Ind. (1905), 12, 150-52. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. Author proceeds to the glycerine determination according to the monacetine
method similarly like LEWKOWITSCH (Chem. - Ztg. vo. 1889, I. pg. 659) for the analysis of lower caustic solutions. A
quantity of glycerine water = about 10 g pure glycerol, is event. with baryte water, neutralized, with that 3 to 4 part
volumes alcohol and that 1 1/2 part volumes ether shifts, after which settling filters, with alcohol-ether washed afterwards,
the filtrate on the water bath evaporated and, if no smell after alcohol more perceptibly, the vaporization still about 20
minutes continued. The evaporated glycerine mixtures is weighed and determined from that averages of two samples,
which were acetylated after the usual procedure, the glycerol content. With presence of only small organic additions also
the direct vaporization of the glycerine water without previous precipitation with alcohol-ether supplied good results.
Since the monacetine method is however no particularly comfortable despite their advantages, author has recently from
SHUKOFF and SCHESTAKOFF (Z. f. angew. CH. vo. 18, pg. 294; C. vo. 1905, I. pg. 1051) indicated extraction method
with the values received in the monacetine procedure compared and generally good agreement found, even if the
extractions proceeded supplied regularly to high values. A disadvantage of the latter is that it requires the most favorable
case in 9 hours time.
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18. Over Caryophyllin. [machine translation]

By Meyer, Hans; Hoenigschmid, Otto
From Monatshefte fuer Chemie (1905), 26, 379-89. Language: Unavailable, Database: CAPLUS,
DOI:10.1007/BF01532024
[Machine Translation of Descriptors]. For the preparation of the caryophyllins, one can extract with water and vibrate the
molukkischen cloves also with ethers and clean the separated caryophyllin by NH3; it has the formula (C10H16O)4 =
C40H60(OH)4 and contains probably only primary and secondary groups of alcohols; it forms color-, smell- and tasteless,
silk-glossy needles (from alcohol) of the melting point 295° , undecomposed already sublimates and spreads
frankincense smell with heating up at lower temperature, in the vacuum; it becomes, like also its derivatives, insoluble
with graters strongly electrically, is in water and alkalis, easily soluble in ethene ones and hot alcohol and shows the
LIEBERMANN Cholesterine reaction. With Na-acetate and acetic anhydride, there is the tetra-acetyl derivative,
C40H60(OC2H3O)4, colorless needles (from diluted CH3OH), melting point 268-271° ; against permanganate solutions
caryophyllin is resistant; with registering in fuming HNO3 separates caryophyllin acid, C40H64O12, colorless, in the vague
daylight slowly, in the direct sunlight rapidly yellow to red coloring needles, which do not give the LIEBERMANN
Cholesterine reaction. The acid contains four carboxyl groups. From the silver salt an amorphous alkali soluble and a
crystalline alkali insoluble when heating with excess iodine methyl product is obtained. The latter is the tetramethyl ester,
C40H60O8(OCH3)4, the less complicated from the acid and ether, diazomethane can be prepared; colorless needles (from
90%igem methyl alcohol), with melting point 164-165°. Acetyl caryophyllic acid, from the acid, Na-acetate and acetic
anhydride; colorless needles, (from diluted acetone), with melting point of 200-204° , decomposes cloudily with further
heating up, (206°). From caryophyllin and ether, diazomethane forms the caryophyllin in appearance and solubility
similar product for lower in the beginning of a violent reaction (probably caryophyllin monomethyl ether, colorless
crystals, with melting point of 187°), that with the acetylation mainly acetylmethylcaryophyllin,
(Methyltriacetylcaryophyllin), C40H60(OCH3)(OC2H3O)3, silver-glossy needles, (from CH3OH), with melting results in 212-
213%. With examination of different alcohols on their behavior against diazomethanes, it did not show the tertiary
alcohols, (tertiary butyl alcohol, amyl hydrate, triphenylcarbinol) and the secondary borneol and l-menthols reaction.
Glycerol becomes slowly contested; and the behavior to aldehydes further is studied.
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19. Of the D-Glyceric Acid Derived Ester and Amides of the Dimethoxy Propionic Acid. [machine translation]
By Frankland, Percy Faraday; Gebhard, Norman Leslie
From Proceedings Chem. Soc. (1905), 21, 189. Language: Unavailable, Database: CAPLUS
SciFinder® Page 12
[Machine Translation of Descriptors]. The authors examined already several times, in which way the optical activity of
the D-glyceric acid is affected by the different substitutions. In the same intention, the replacement both the hydroxyl
hydrogen is pursued now by methyl. It points itself that through this a strong increase of the activity is caused, much
more strongly, as to the example by acetylation: [M]D, Glycerine, Diacetyl, Dimethoxy. Acid Glycerine Acid,
Propionic Acid. Methylester ...... -5.76, -24.56, -103.8. Ethyl ester ........,-12.30, -35.56, -114.4.
Propylester ......., -19.15, -45.17, -122.5. iso-propyl ester ....-17.49, -41.69, -. n-butyl ester .......-
21.37, -, -124.2. iso-butyl ester .....-23.05, -50.38, -. sec. - Amyl esters ..-24.85, -50.54,
-. n-heptyl ester ......-23.05, -47.89, -127.9. n-octyl ester .......-22.28, -47.92, -125.6. d-dimethoxy
propionic acid methylester, C6H12O4; from 1 mole d-glyceric aicd methylester, 6 mole CH3I and 3 moles Ag2O in ether
under cooling and eventual heating up Kp15, 77 to 78°. [α]D20 = -69.70°; somewhat soluble into cold water. Ethyl ester,
C7H14O4, Kp17, 92°, [α]D20 = -69.95°. Propylester, C8H16O4, Kp15, 93 to 95°; [α]D20 = -69.01°. Butylester, C9H18O4,
Kp15; 114 to 115°; [α]D20 = -64.88°. Heptylester, C12H24O4, Kp15, 144 to 146°; [α] D20 = -54.84°. Octylester, C13H26O4,
Kp15, 157 to 158°; [α]D20 = -50.46°. Dimethoxypropion amide, C5H11O3N. From the ethyl ester and NH3 in methyl
alcoholic solution with 0°. Needles from methyl alcohol, melting point 77 to 77.5°. [α]D20 = -54.55° (p = 3.1283 in
methyl alcohol), -71.60° (p = 1.6956 in pyridine). Dimethoxypropion methylamide, C6H13O3N. From the butyl ester and
methylamine into alcoholic solution. Fibrous mass from rending petroleum ether. [α]D20 = -58.72° (p = 1.8918 in methyl
alcohol). In the end, the authors examine still in detail the influence of the temperature on the turn of the indicated
esters. In all cases decreases the turn at rising temperature, and the value decreases for itself for all esters worth [M]D
around 0.16 per ° of temperature.
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20. Of the D-Glyceric Acid Derived Ester and Amides of the Dimethoxy Propionic Acid. [machine translation]
By Frankland, Percy Faraday; Gebhard, Norman Leslie
From Journal of the Chemical Society (1905), 87, 864-78. Language: Unavailable, Database: CAPLUS
[Machine Translation of Descriptors]. The authors examined already several times, in which way the optical activity of
the D-glyceric acid is affected by the different substitutions. In the same intention, the replacement both the hydroxyl
hydrogen is pursued now by methyl. It points itself that through this a strong increase of the activity is caused, much
more strongly, as to the example by acetylation: [M]D, Glycerine, Diacetyl, Dimethoxy. Acid Glycerine Acid,
Propionic Acid. Methylester ...... -5.76, -24.56, -103.8. Ethyl ester ........,-12.30, -35.56, -114.4.
Propylester ......., -19.15, -45.17, -122.5. iso-propyl ester ....-17.49, -41.69, -. n-butyl ester .......-
21.37, -, -124.2. iso-butyl ester .....-23.05, -50.38, -. sec. - Amyl esters ..-24.85, -50.54,
-. n-heptyl ester ......-23.05, -47.89, -127.9. n-octyl ester .......-22.28, -47.92, -125.6. d-dimethoxy
propionic acid methylester, C6H12O4; from 1 mole d-glyceric aicd methylester, 6 mole CH3I and 3 moles Ag2O in ether
under cooling and eventual heating up Kp15, 77 to 78°. [α]D20 = -69.70°; somewhat soluble into cold water. Ethyl ester,
C7H14O4, Kp17, 92°, [α]D20 = -69.95°. Propylester, C8H16O4, Kp15, 93 to 95°; [α]D20 = -69.01°. Butylester, C9H18O4,
Kp15; 114 to 115°; [α]D20 = -64.88°. Heptylester, C12H24O4, Kp15, 144 to 146°; [α] D20 = -54.84°. Octylester, C13H26O4,
Kp15, 157 to 158°; [α]D20 = -50.46°. Dimethoxypropion amide, C5H11O3N. From the ethyl ester and NH3 in methyl
alcoholic solution with 0°. Needles from methyl alcohol, melting point 77 to 77.5°. [α]D20 = -54.55° (p = 3.1283 in
methyl alcohol), -71.60° (p = 1.6956 in pyridine). Dimethoxypropion methylamide, C6H13O3N. From the butyl ester and
methylamine into alcoholic solution. Fibrous mass from rending petroleum ether. [α]D20 = -58.72° (p = 1.8918 in methyl
alcohol). In the end, the authors examine still in detail the influence of the temperature on the turn of the indicated
esters. In all cases decreases the turn at rising temperature, and the value decreases for itself for all esters worth [M]D
around 0.16 per ° of temperature.
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21. For the knowledge of the sperm whale trance. [machine translation]
By Fendler, G.
From Chemiker-Zeitung (1905), 29, 555-56. Language: Unavailable, Database: CAPLUS
SciFinder® Page 13
[Machine Translation of Descriptors]. Author could examine a larger quantity of pure sperm whale trance, from Physeter
macrocephalus. From the Tran 15% raw spermaceti were formed, to melting point 42°, Density 150.942, sign. 134,0,
iodine number of 9.3, content of unsaponifiable substance 51.1%, melting point of these alcohols 45°. The liquid portion
of the trance, the whale or Spermaceti oil have D20. 8781, solidification point 15,5°, Melting point 18,0°, RMZ. 0,60, sign.
150,3, iodine number of 62.2, unsaponifiable 39.2%, acid value 13.2 = 6.6% oleic acid. To the complete saponification
had to be expanded the heating with alcoholic KOH on the water bath against 6 hours. The cold saponification after
HENRIQUES is to be preferred with the Spermaceti oil. The separated alcohols had D40. 8379, melting point 32,5°,
Solidification point 30,5°, Iodine number of 46.7, acetyl number 200.4, melting point of the acetylated alcohols 15°. Fatty
acid, D15 had a brown-yellow oily liquid. 8999, melting point 18,8°, Solidification point 12,4°, Sign. 236,2, iodine number
of 68.64, acetyl acid number 222.5, acetyl saponification number 240.4, acetyl number/value 17.9, middle mole 237,7,
content of liquid fatty acid 85.8, at solid fatty acid 14.2%. In the oil glycerol was proven with security, so that the relevant
indication of HOFSTADTER(LIEBIG's Ann. 91. 177), was doubted for correctness of ALLEN and LEWKOWITSCH, was
confirmed. The glycerol content was determined to 1.32%, so that from now on the presence of glycerol cannot come
any more than signs of a falsification of the adequate sperm oil.
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22. The Analysis of Crude Glycerol. Methods Recommended by the International Committee
By Anon.
From Chimiste (1911), 2, 163-5,178-81. Language: Unavailable, Database: CAPLUS
SciFinder® Page 14
The older method of sampling by thrusting a glass tube into the container is replaced with a sampler made of 2 brass
tubes 1 fitting inside the other which are perforated throughout their length (thus making it possible for the glycerol to flow
in at all points). The sampler is closed by rotating the 1 tube in the other. (1) Detn. of free caustic alkali: 20 g. sample in
100 cc. flask, dil. with 50 cc. freshly distilled H2O, add excess of neutral BaCl2 soln., 1 cc. phenolphth., fill to the mark,
shake, settle, draw 50 cc. of supernatant liquid and titrate with 1 N acid. Calc. to % Na2O. (2) Detn. of ash and total
alkali: Place 2-5 g. sample in a Pt dish, ht. with low flame and when carbonized to the point that the H2O is no longer
colored by sol. organic compds. lixiviate with hot distilled water, filter, wash and ignite the residue in a Pt dish. The
filtrate and wash water are evapd. in the Pt dish, ignited below fusion, and weighed, dissolve in H2O and titrate for alk.
using Me-orange in the cold, or litmus at boiling. (3) Detn. of alkali present as carbonate: 10 g. sample dil., with 50 cc.
H2O add 1 N acid sufficient to neut. alk. detd. according to (2), boil 15-20 mins. under reflux condenser, wash the
condenser tube down with H2O and titrate back with 1 N NaOH using phenolphth. From this calc. Na2O, deduct (1),
difference is Na2O as Na2CO3. (4) Detn. of alk. combined with organic acids: The sum of (1) and (3) minus (2) gives this
value. (5) Detn. of the acidity: 10 g. dild. to 50 cc. with H2O, titrated with 1 N NaOH using phenolphth. Expressed as g.
Na2O necessary to neutralize 100 g. (6) Detn. of total residue at 160° C.: For this detn. the crude glycerol should be
slightly alk. with Na2CO3 (not more than the equiv. of 0.2% Na2O) to prevent loss of organic acids, and not more to
prevent polymerization. 10 g. placed in 100 cc. flask dil. with H2O and 1 N HCl or Na2CO3 to give required alkalinity, fill
to mark, mix, take 10 cc., place in Petrie or similar dish (2.5 in. diam., 0.5 in. deep). In case org. residue is high take
enough to give no more than 30-40 mg. Evap. first on top of 160° oven, then inside. Most of the glycerol should be
evapd. at 130-40° with the door partly open. When only a slight vapor is formed, remove and cool, add 0.5-1.0 cc. H2O,
rotate to dissolve all or part of the residue and evap. again until it will not spit any longer (usually 2-3 hrs.). Then ht. 1 hr.
longer at 60°, remove, cool, treat with H2O and evap. and heat as before, cool in desiccator over H2SO4 and weigh. The
treatment with H2O, etc., is repeated until a const. loss of 1-1.5 mg. per hr. is obtained. Corrections to be applied to the
wt. of the total residue: In acid glycerols correct for alk. added (1 cc. 1 N NaOH = 0.022 g.). In alk. glycerol correct for
acid added to change NaOH and Na2CO3 to NaCl. Corrected wt. × 100 = % residue above 160°. Save residue for detn.
of non-volatil acetylizable impurities. (7) Organic residue: Subtract ash from total residue at 160°; report as org. residue
at 160°. (8) Moisture: 2-3 g. dry bulky asbestos free from acid-sol. impurities is placed in a 15 cc. weighing bottle, the
whole weighed, 1-1.5 g. sample dropped on the asbestos, weigh again and place in H2SO4, vacuum desiccator (1-2 mm.
Hg). The detn. requires 48 hrs. or more. Aceti process for glycerol detn.: The method is to be used (if applicable) when
only 1 method is used. The sample should not contain over 50% H2O. Reagents required are: (A) best acetic anhydride
(should require not more than 0.1 cc. 1 N NaOH to saponify impurities in 7.5 cc.); (B) fused NaOAc (fuse without
charring); (C) 1 N NaOH (about) free from Na2CO3; (D) standardized 1 N NaOH (carbonate-free): (E) 1 N acid; (F)
phenolphth. soln. (0.5% in alc. and neutralized). Method: Into a 120 cc. narrow mouthed flask weigh 1.25-1.5 glycerol,
add 3 g. NaOAc (anhyd.) then 3 g. Ac2O, connect flask with 50 cm. Liebig condenser by ground glass joint or rubber
stopper (if rubber should first be treated with Ac2O vapor), boil 1 hr., cool somewhat, add 50 cc. H2O at 80° through
condenser, cool flask and contents, when cold wash down condenser, etc., with water, remove flask, filter through acid-
washed filter into 1 l. Jena glass flask, wash thoroughly with H2O, add 2 cc. of (F) then (C) or (D) until faint pinkish
yellow color appears and finish carefully, add 50 cc. or calc. amt. of (D) (noting the exact amt.), boil 15 mins., cool quickly
and titrate excess alk. with (E) to chosen end-point. From the 1 N NaOH used calc. % glycerol after making correction
for the blank test using the same materials without the sample, 1 cc. 1 N NaOH = 0.03069 g. glycerol. Detn. of glycerol
value of the acetylizable impurities: The residue obtained above dissolved in 1-2 cc. H2O placed in a 120 cc. flask and
evapd. Proceed as above and calc. to glycerol. Bichromate process for glycerol detn.: Reagents. (A) pure K2Cr2O7,
powdered and dried at 110-20°; (B) dil. K2Cr2O7 soln. = 7.4564 g. (A) dissolved to make 1 l. at 15.5°; (C) dissolve 3.7282
g. (A) in 50 cc. H2O, add 50 cc. of 50% H2SO4 (by vol.), cool, add moderate excess Fe(NH4)2(SO4)2 from weighing bottle
and titrate back with (B); (D) Ag2CO3 is prepared as required from 140 cc. of 0.5% Ag2SO4 soln. by pptg. with about 4.9
cc. 1 N Na2CO3 soln., wash by decantation; (E) subacetate of Pb, boil a 10% soln. of c. p. Pb(OAc)2 with excess PbO for
1 hr. keeping vol. const. and filter hot. Disregard any ppt. subsequently formed and keep away from CO2; (F) K3Fe(CN)6,
a 0.1% soln. Method of analysis: Weigh 20 g. glycerol, dil. to 250 cc., take 25 cc., add Ag2CO3, shake occasionally, after
10 mins. add slight excess (usually about 5cc.) of (E), in a few mins. dil. to 100 cc. with H2O then add 0.15 cc. to
compensate for the ppt., filter through dry filter, test filtrate with (E) to see if more ppt. forms. If so start with a fresh
portion and use 6 cc. of (E). Take 25 cc. of the filtrate add 12 drops of H2SO4 (1 : 4) to ppt. PbSO4, then 3.7282 g. (A),
rinse down with 25 cc. H2O, dissolve all K2Cr2O7, add 50 cc. of 50% H2SO4, heat in boiling water for 2 hrs., add excess
Fe(NH4)2(SO4)2 (C) from weighing bottle, making spot tests on porcelain plate with (F), titrate back with dil. K2Cr2O7.
From K2Cr2O7 used calc. % glycerol; 1 g. K2Cr2O7 = 0.13411 g. glycerol. Instructions for calc. actual glycerol Content:
(1) Det. the apparent % of glycerol by the acetin process as described. The result will include acetylizable impurities if
any be present. (2) Det. the total residue at 160°. (3) Det. the acetin value of the residue in (2) in terms of glycerol. (4)
Deduct the result found in (3) from the % obtained in (1) and report this corrected figure as glycerol. Notes: In crude
glycerol of good com. quality the sum of H2O, total residue at 160°, and corrected acetin result comes to within 0.5% of
100% K2Cr2O7 agrees with acetin result within 1%. If differences are greater polyglycerols or trimethylene glycol are
present. The latter is more volatil and can be conc. by distillation. The approx. amt. can be detd. by the "spread"
between the results. By acetin method trimethylene glycol shows 80.69%, by K2Cr2O7 138.3% when expressed as
glycerol. Detn. of sulfides, sulfites and thiosulfates were not included in this report. Recommendations: If the non-volatil
org. residue at 160° in a soap-lye crude glycerol is over 2.5%, i. e., when not corrected for CO2 in the ash, then the
residue shall be examined by the acetin method and any excess of glycerol over 0.5% deducted from the acetin figure.
In saponification, distillation and similar glycerols, the limit of organic residue which should be passed without further
exam. shall be 1%. If the sample contains more than 1% the residue must be acetylated and any glycerol found (after
making the deduction of 0.5%) shall be deducted from the % of glycerol found by the acetin test.
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By Anon.
From Journal of the Society of Chemical Industry, London (1911), 30, 556-8. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 16
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SciFinder® Page 17
By Anon.
From Pharmaceutical Journal (1911), 82, 522. Language: Unavailable, Database: CAPLUS
SciFinder® Page 18
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By Anon.
From Chemical News and Journal of Industrial Science (1911), 103, 2201-1,233-5. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 19
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26. Cotton Wax
By Knecht, Edmund; Allan, John
From Journal of the Society of Dyers and Colourists (1911), 27, 142-6. Language: Unavailable, Database: CAPLUS
Cotton wax was first isolated by Schunk, 1868, who obtained 0.004%. With modern methods the authors have repeated
the extraction of cotton, using a Soxhlet app., first with petroleum ether, and then with benzole, and the wax which it
contained was obtained in 2 fractions. The 1st product was an odorless, dull yellow substance, closely resembling
beeswax in tecture and fracture. When repeatedly treated with b. 96% alc., 18.82% of an insol., glassy wax was left, m.
78°, I no. 11.28. The portion sol. in alc. was more plastic, m. 62°, I no. 33.42. When boiled with 0.5 N glycerol NaOH
soln., it was found to contain 47.5% unsaponifiable matter, m. 67-8°. Upon acetylation 2 hydrocarbons of cryst. form
were obtained, one m. 68. 1°, and giving on analysis results indicating hentriacontane (C31H64), and the other m. 70° and
agreeing in analysis with dotriacontane. From the acetylated alc. a crop of crystals sepd. on cooling its alc. soln. They
melted at 127.2°, and the substance was evidently a phytosterol. By sepg. and acidifying the saponified portion of the
wax 0.21% of glycerol was isolated, a small quantity of an acid m. 74.4°, and stearic and palmitic acids. The fraction of
wax obtained from benzole was a dark green granular mass m. 68°, acid no. 4.03, sapon. no. 83.3. The unsaponified
matter yielded 33.55% of a reddish brown sticky wax, m. 63.4°. Upon acetylation a considerable quantity of a phytosterol
acetate, m. 122.4°, was obtained. From the fatty acids obtained from the saponified portion was sepd. a small quantity of
cryst. acid m. 70.8°, and having a mean mol. wt. of 455. This is possibly melissic acid (C30H60O2).
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27. Ricinstearolic Acid

By Muhle, Georg
CAPLUS
Ricinstearolic acid diiodide, Me(CH2)5CH(OH)CH2CI : CI(CH2)7CO2H, obtained in 50-60% yield by allowing the acid to
stand with 2 ats. I in 20 parts CS2 and 1% of dry FeI2 for 2 months in the dark, needles, m. 62°, turns brown 130-40°,
decomp. 175°. If the acid is treated in AcOH with I at 70-80° (Arnaud and Posternak, C. A., 3, 2678), the HO group is
acetylated and polymerization takes place, but by warming the resulting dark oil with Na2CO3 (8 g. cryst. salt in 250 g.
H2O) the above diiodide is obtained in 80% yield; if the temp. is kept below 40°, the acetylation and polymerization do not
take place and the yield of iodide is quant. The same result is obtained after 10 hrs. at room temp. Dil. b. KOH removes
the I, dil. KMnO4 oxidizes the iodide even in the cold. Sodium salt, needles; barium salt, silky needles; mercury salt, light
yellow, powdery ppt.; methyl ester, faintly yellow oil, decomp. 150°. Contrary to the statements of Krafft (Ber., 21, 2735)
and Mangold (Monatsh., 15, 308) ricinoleic and ricinelaidic acids are not converted into different acids on distillation in
vacuo; the former b10 226-8° without decomp., partial decomp. beginning only under 60 mm.; the latter m. 51-2°, b10 240-
2° without decomp. Acetylricinelaidic acid, from the HO acid and 2.5 parts Ac2) 1 hr. at 150°, light yellow, viscous oil.
Acetylricinstearolic acid. Methyl ricinstearolate, from the acid and a b. 3% MeOH soln. of HCl or alk. Me2SO4, oil, d.
0.9389. Ethyl ester, b12 230°, d. 0.9371. Monoricinstearolylglycerol, from the Na salt of the acid (3.3 g.) and 1 g.
CH2ClCH(OH)CH2OH 6 hrs. at 150° in a CO2 atm., faintly yellow, viscous oil. Triricinstearolylglycerol, from 1.9 g.
CHCl(CH2Cl)2 and 13 g. Na salt 10 hrs. at 190-200° in a sealed tube, yellow, viscous oil. Monochlorostearolic acid, from
4 g. of the ricinstearolic acid and 6.5 g. PCl5, faintly yellow viscous oil, decomp. on distillation, even in vacuo.
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28. Analysis of Fats

By Madinaveitia, Antonio
From Anales de la Real Sociedad Espanola de Fisica y Quimica (1913), 10, 153-66. Language: Unavailable,
Database: CAPLUS
The high results obtained by the method of Zeisel and Fanto are attributed, in part, to the incomplete evapn. of MeOH
after sapon. M. omits sapon. by alc. KOH and proposes the following modified method in which sapon. is accomplished
by HI. The weighed fat (not more than 0.3 g.) and 10 cc. HI (d. = 1.8) are placed in the Zeisel app. and the temp. is
gradually raised (so as to avoid evolution of HI) to 100-100° (oil bath). This temp. is maintained until the AgNO3 soln.
becomes clear (deposition of ppt.), after which the temp. is kept at 140° for 1 hr.; the current of CO2 through the app. is
then discontinued and the Ag salt is detd. as usual. This method gives more accurate results than the original one and
has the advantage of avoiding the preliminary sapon. and of employing smaller amts. of fat. The method of Lewkowitsch
for direct detn. of free OH in fats by acetylation was also examd. Application of this method to tristearin showed that
acetyl entered the mol. in an amt. (measured by the AcOH produced) which indicated the formation of acetodistearin plus
a mol. of stearic acid. When the product of the reaction was dissolved in Et2O and the soln. shaken with dil. K2CO3 soln.,
a subst. remained in the Et2O layer which yielded 13.73% glycerol (by M.'s modified method), as compared with 13.81%
glycerol calc. for acetodistearin. This reaction of Ac3O with satd. fats explains the poor results obtained with the
Lewkowitsch method.
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29. Chemistry of starch. II. Schardinger's crystallized dextrins

By Pringsheim, Hans; Eissler, Franz
CAPLUS, DOI:10.1002/cber.19130460370
cf. C. A., 7, 345. S.'s cryst. dextrins can be pptd. not only by Et2O or CHCl3 but also by C6H6, PhMe, o-C6H4Me2, PhBr,
PhNO2, or petroleum ether; CHCl3 works best, however, but the pptn. is not complete; by adding petroleum ether to the
filtrate from the CHCl3 ppt. and allowing to stand 24 hrs. in the ice chest, a further yield of 10-20% can be obtained; from
the ppts. the solvents can be washed out with alc. without destroying the cryst. structure. From an aq. soln. of these
dextrins sufficiently dil. to hold the α- and β-compds. in soln. there seps. 3rd dextrin (a) (S.'s "Schlamm"), which can be
filtered only with the greatest difficulty, as it clogs the filter, and was, therefore, centrifuged (yield, 5 g., with 70 g. of α-
and 12 g. of β-dextrin); it forms 6-sided tables, (C6H10O5)2x.EtOH, [α]D 20 139.2° (1.5% aq. alc.). Like α-dextrin (tetra-
amylose), with ZnCl2 and Ac2O it gives diamylose hexa-acetate, showing that it belongs to the α-series. Similarly, both it
and α-dextrin with BzCl and dil. NaOH give diamylose dibenzoate, while β-dextrin (hexa-amylose) gives triamylose
tribenzoate. Again, (a), di- and tetraamyloses give with I-KI in hot H2O green needles and tri- and hexa-amyloses dark
red-brown prisms; the former, when air-dried and moistened with H2O, give a transient blue color changing to dark red on
addition of more H2O. These iodine addition products are hygroscopic; those from hexa- and tetra-amylose have the
comp. (C6H10O5.)6.2I and (C6H10O5)4.1.5 I, resp. P. and E. believe (a) to be a hexa- or octosaccharide, consisting of 3 or
4 diamylose mols. connected, like polymeric compds., by secondary valences. Tetra-amylose. heated 0.5 hr. at 200° in 7
parts glycerol, gave (a) and a β-(tri- or h.xa-) amylose. If, in the acetylation of tetra-amylose, H2SO4 is used instead of
ZnCl2 as catalyst and the temp. raised to 115°, there is obtained the hexa-acetate, amorphous powder, decomp. 155°,
[α]D 24 128.9°, of isodiamylose, amorphous hygroscopic powder, decomp. about 200°, [α]D 21 168.3°. reduces Fehling
soln., is no longer pptd, from H2OCHCl2, and other org. solvents, gives only a brown-red soln. but no cryst. ppt. with I,
gives no osazone, is decompd. by emulsin into glucose but is not attacked by diastase or yeast. P. and E. conclude that
there has been no opening of the ring but a shifting of the unions between the glucose molecules, thus [R =
HOCH2CH(OH)]: In the same way, from hexa-amylose was obtained the nono-acelate, decomp. 138°, [α]D 24 130.1°, of
isotriamylose, turns brown 190°, decomp. 203°, [α]D 24 173.3°. In the attempt to obtain amyloses without the aid of
bacteria, Zulkowsky's sol. starch (Ber., 13, 1395) was acetylated by Pregl's method (Monatsh., 32, 1049) with Ac2O and
a little H2SO4 in the cold; the dextrin obtained from this by sapon. gave on further acetylation with ZnCl2 a non-reducing
acetate whose mol. wt. corresponded to 12 glucose residues. By acetylation of the sol. starch with H2SO4 at 115° was
obtained a triamylose nono-acetate, [α] 129.7°; the sugar obtained from it reduced as strongly as isotriamylose and
showed [α] 175.2°. The acetate, however, was not homogeneous; it gave a fraction difficultly sol. in Et2O which showed
[α] 140.6°. By the sep. fermentation by means of Bacillus macerans of amylopectin and amylose (Gruzewska, J. physiol.
path. on., 14, 7), both α and β-dextrins were obtained from each in about the same proportions, and P. and E. believe
that the a-compd. is a secondary degradation product of the β-compd. Neither α- nor β-dextrin, di- nor triamylose is
decomp. by yeast, maltin, phtyalin, pancreas juice; a decomp. was effected by some mold fungi, takadiastase, the
ferment of Aspergillus orycae, but it always proceeded as far as glucose.
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30. Alfalfa. VI. Alfalfa seed oil

By Jacobson, C. A.; Holmes, August
From Journal of the American Chemical Society (1916), 38, 480-5. Language: Unavailable, Database: CAPLUS,
DOI:10.1021/ja02259a033
cf. C. A. 8, 3827. The seeds showed 3.43% ash, 11.39% Et2O ext., 10-52% crude fiber, 6.35% moisture, 32.43%
carbohydrates, etc., and 35-88% crude protein. For extn. of large amts., gasoline, b645 65-95°, was used instead of
Et2O, the yield of ext. being only 1.92% less. The oil thus obtained showed n17 1.4783 to n69 1.4587, d4 24 0.9117,
sapon. no. 172.3, 1 no. 154.2, acid no. 2.85, acetyl value 19.8, Reichert-Meissl no. 0.40, unsaponifiable matter 4.40%,
glycerol 1.97%, sapon. no. of acetylated oil 192.2. There are practically no volatile fatty acids and no lactones in the free
acids; 92.5% of the oil consists of insol. fatty acids (from lauric upwards) with a neutralization value 191.5, mean mol. Wt.
293, sapon, no. 189.9, 1 no. 169.5, giving 17% solid bromides by the Hehner-Mitchell test. They consist of 90.4% liquid
and 9.6% solid acids. The liquid acids consist of oleic, linoleic and linolenic acids (in the proportion of 3.3, 73. 2 and
23.5%, resp., calcd. from the oxidation products) and the solid acids of carnaubic, daturic and possibly behenic acids.
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31. 1,1-Diarylglycerols
By Paal, C.
CAPLUS, DOI:10.1002/cber.19160490209
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cf. C. A. 1, 2109. The 40% yield of 1,1-diphenylglycerol (a) obtained by the method described in the earlier paper is
increased to 60% by using for 5 g. Me glycerate 5 g. Mg, 32.1 g. PhBr, and 80 g. Et2O. Heating with alc. NH3 for a long
time at 210° does not affect (a). From 1.5 parts (a) in 5-6 parts cold C5H5N treated dropwise with 2 parts AcCl and
allowed to stand a long time is obtained 2 parts of the 2,3-diacetate, 1.3 parts of which are also obtained from 1 part (a)
boiled 45 min. under a reflux with 5 parts Ac2O; it seps. from aq. alc. in elongated leaflets or flat needles, m. 129-31°,
from C6H6-petr. ether in fine needles, from abs.alc. in tables, from supersatd. aq. alc. solns. containing Et2O in short
prisms. Dibenzoate, from (a) in cold C5H5N treated drop by drop with 3 parts BzCl and allowed to stand a long time,
needles from C6H6-petr. ether, m. 180°. When 3 g. (a) in 50 cc. Me2CO are treated with 2.8 g. KMnO4 in 75 g. H2O in
small portions, the filtrate from the MnO2 gives a Ag mirror with NH3-AgNO3, indicating the presence of glyceraldehyde.
After most of the Me2CO has evapd. in the air the milky liquid is distd. with steam, which removes Ph2CO; the residue
from the steam distn. on concn. on the H2O bath deposits a small amt. of unchanged (a) and the neutralized filtrate yields
with basic Pb acetate a copious ppt. of basic Pb glycolate; no (CO2H)2 is present. When 1 part (a) is boiled 15 min.
under a reflux with 10 parts of 20% H2SO4 it goes over into an almost H2O-insol. yellow oil which is extd. with Et2O and
after removal of the Et2O is kept a long time below O°. There results a cryst. mass, satd. with oil, which is best removed
by rubbing with cold aq. alc. The cryst. crude product (15-20% of the (a) used), m. around 113-7° and is easily sol. in all
ordinary solvents except petr. ether, and all attempts to sep. this mixt. (b) into its components by treatment with small
amts. of cold C6H6, MeOH or EtOH failed. If it is taken up in a little Me2CO, treated with alc. and, after warming, with a
little H2O and allowed to stand, there sep. white needles (0.3 7g. from 1.5 g. crude product), which m. 124-45°,
depending on the rate of heating, although the m. p. itself is quite sharp, recrystn. in the same way yields white needles,
m. 135-6° on slow and 142° on rapid heating; their compn. agrees quite well with that of a compound, C30H26O3,
corresponding to 2 mols. (a) minus 3 mols. H2O. Acetylation of (b) with Ac2O yields a yellow oil of aromatic odor which
could not be crystd.; oximation in alc. with aq. NH2OH.HCl and soda, after 2 hrs. boiling under a reflux, yields, on evapn.
of the alc., a cryst. mass satd. with oil which can be removed with petr. ether; the residue, after several recrystns. from
dil. EtOH + Et2O, then from petr. ether, gives an oxime, C15H13ON, flat needles from alc., tablets from C6H6-petr. ether,
m. 109-11°; the mother liquors yield considerable amts. of an oxime mixt. of lower and indefinite m. p. From (b), warmed
under a reflux in alc. with concd. aq. NH2CONHNH2.HCl and soda in excess, then cautiously concd., washed with H2O
and crystd. 4 times from dil. alc. is obtained a semicarbazone, C16H17O2N3, prisms, m. 207-8° (decompn.); the mother
liquors yield a mixt. from which C6H6 at room temp. exts. a more sol. part sepg. in long pointed prisms, m. 158-60°, which
seem homogeneous, but analysis (C 71.41, H 6.26%) indicates that they are still a mixt. of a little of the above
semicarbazone of a mono-anhydro compd. with much of a dianhydro derivative semicarbazone, C16H15ON3; the
behavior of (b) towards NH2CONHNH2 indicates that it contains at least 3, if not 4, anhydro compds. which react with
NH2CONHNH2. Oxidation of (b) in 30 parts Me2CO with 2.86 parts KMnO4 in 20 parts H2O added in small portions at
room temp. gives considerable Ph2CO, removed by steam distn. after evapn. of the Me2CO by cautious warming; the
residue from the steam distn. on acidification gives an oil which is extd. with Et2O; the ext. on evapn. deposits a mixt. of
prisms and needles melting in boiling H2O and dissolving on further addition of H2O and sepg. on cooling in needles, m.
120-31° which can be distd.; the distillate crysts. on cooling, dissolves in alkali and on acidification yields a mixt. of
prisms and long needles, m. 133-41°, containing 76.36% C and 5.92% H. Heated with concd. H2SO4, this mixt. gives no
anthraquinone, indicating the absence of o-BzC6H4CO2H. Treatment with a little cold C6H6 seps. the mixt. into a sol.
part, sinters 98°, m. 126-43°, and an insol. part, m. 125-40°. Each was dissolved in dil. NH4OH, freed from excess of
NH4OH by heating and treated hot with CaCl2; the C6H6-sol. part at once deposited a difficultly sol. pulverulent Ca salt
while the C6H6-insol. part gave only after some min. a cryst. (needles) salt; a hot HCl soln. of the 1st salt on cooling
quickly yields an acid in short needles, m. 155-7°, while that of the 2nd only after several hrs. deposits an acid in long,
slender needles, m. 144-7°. The oily dehydration products (c) accompanying (b) which are removed from (b) by means
of dil. alc. (see above) are insol. in cold H2O, difficultly in petr. ether, easily in almost all other org. solvents. They form
about 80% of the (a) used. They contain 82.51% C and 6.21% H and probably consist of about equal parts of a mono-
and a di-anhydro compd. Oximation yields the oxime C15H13ON, m. 109-10° (see above); by repeatedly treating the
reaction product, after extn. with Et2O, with dil. NaOH, it is possible to remove a small amt. of an oxime pptd. by acids in
milky form, sol. in Et2O and sepg. from dil. alc. in long, flat, silky needles, m. 141-3°, quite unstable changing after 2 days
in the desiccator into a greenish oil. Treatment of (c) with NH2CONHNH2 gave chiefly oily products, with a small amt. of
the semicarbazone, m. 206-7° (see above). Oxidation of (c) with KMnO4 gives much Ph2CO and a small amt. of a mixt.
of acids which are in part quite unstable and not identical with those obtained from (b). Fractional distn. of (b) gave 53%
of an oil, b20 176-8°, which reddens fuchsin-SO2, reduces NH2-AgNO3 and forms a cryst. addition product with NaHSO3;
in spite of its const. b. p., analysis (C 84.60-84.81, H 6.05-6.07%) shows that it is not homogeneous but is probably a
mixt. of a mono- and a dianhydro deriv., the latter predominating. Decompn. of the NaHSO3 compd. with dil. H2SO4
gives a yellow oil which, on extn. with Et2O, evapn. of the Et2O, removal of the oil from the cryst. portion of the residue by
means of petr. ether, crystn. from C6H6-petr. ether, dil. alc. and finally Me2CO-petr. ether, yields a compound, C15H14O2,
needles, m. 181-3°, does not redden fuchsin-SO2. Under 30 mm. 6 g. (c) yields 3.4 g. oil b. 200-5°, which reddens
fuchsin-SO2 and gives with NaHSO3 a partly cryst. addition product; the non-cryst. portion of this yields an oxime, m.
138-41°, which, however, is not homogeneous, judging from the analytical results; from the cryst. NaHSO3 compd. is
obtained a small amt. of a substance sepg. from C6H6-petr. ether in flat needles, m. 169-71°, insol. in alkalies, does not
reduce NH3-AgNO3, does no redden fuchsin-SO2, not attacked by KMnO4 in Me2CO at room temp. dl-I,I-p-Ditolylglycerol
is obtained in about 1 g. yield from 5 g. Mg, 35.6 g. p-MeC6H4Br and a granule of 1 in 50 g. Et2O treated drop by drop
with 5 g. Me dl-glycerate suspended in C6H6-Et2O, boiled 1 hr., allowed to stand 12 hrs., decompd. with ice and dil.
H2SO4, sepd. from the aq. layer, dried, freed from most of the Et2O, cautiously treated with petr. ether, freed from most of
the oily and resinous impurities by spreading on clay and repeatedly crystg. from C6H6-petr. ether, dissolved in Me2CO,
cautiously dild. with H2O to ppt. the impurities and finally crystd. from dil. alc.; it seps. in needles, m. 116-7°. dl-I,I-
Dibenzylglycerol, similarly prepd. from PhCH2Cl (yield, 15%), needles, m. 93-4°.
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32. Modifying solubilities of acetylcellulose

By Knoevenagel, E.
From No Corporate Source data available (1917), US 1241995 19171002, Language: Unavailable, Database:
CAPLUS
Acetylcellulose insol. in acetone is rendered sol. by dissolving it in an acetylating mixt. or treating it with H2O, alc.,
glycerol or other weak hydrolyzing substance and heating at a temp. of about 70-100° until the desired change in soly.
has been produced.
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33. The specific gravity and index of refraction of glycerol solutions

By Wolff, Hans
From Angewandte Chemie (1919), 32(I), 148. Language: Unavailable, Database: CAPLUS
cf. C. A. 13, 3031. "Examn. of a glycerol of known purity, by detd. titration with dichromate and by acetylation, gave sp.
gr. of satisfactory agreement with Gerlach's tables, and for a glycerol content of about 77%, also with Skalweit's tables.
Investigations of the indices of refraction gave satisfactory agreement with Skalweit's tables, but cast much doubt on the
values given by Lenz and Strohmer; the sp. gr. given by the latter are also in poor agreement. The coeff. of expansion of
an approx. 77% glycerol was 0.00046; the changes of n for 1° were 2.8 × 10-4 and 2.6 × 10-4 for 86% and 77% glycerol,
resp."
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34. Tannin and the synthesis of similar substances. VI

By Fischer, Emil; Bergmann, Max
From Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen (1919), 52B, 829-54. Language:
Unavailable, Database: CAPLUS
SciFinder® Page 25
cf. C. A. 13, 1466. The hydrolysis of Ac derivs. with HCl in MeOH instead of alkalies described in the earlier paper can
be applied to other substances where the product is sensitive to alkalies. Thus 5 g. o-AcOC6H4CO2H in 50 cc. MeOH
kept 4 hrs. at 18° with 5 cc. aq. HCl (d. 1.19), dild. with 100 cc. H2O and freed from the excess of MeOH in vacuo at room
temp., yields 3.2 g. HOC6H4CO2H; and again, from 2 g. hydrated triacetylgallic acid in 20 cc. MeOH kept 2 hrs. at room
temp. with 2 cc. HCl are obtained 1.02 g. hydrated gallic acid. Penta-m-digallyl-β-glucose, obtained in 2.8 g. yield by
letting 5 g. of the Ac compd. in 50 cc. Me2CO stand 24 hrs. at 15-20° with 50 cc. MeOH and 7 cc. HCl (d. 1.19), dilg.
somewhat with H2O, treating with 75 cc. N NaOH, evapg. off most of the MeOH and Me2CO in vacuo, adding a little dil.
H2SO4, taking up the brown viscous product in AcOEt, washing several times with H20, evapg. in vacuo and repeating
the treatment with Me0H-HCl, is an amorphous tannin-like substance, with [α]D 18 10.8° (about 5% soln. in alc. or
Me2CO); the products obtained before by alk. hydrolysis at 0° showed [α]D 13-18° and agree in other properties with the
new product. A 0.2% soln. cooled below 30° shows a quite marked milky turbidity and only when it contains 0.1% at
most does it remain clear at 20°; such a soln. rotates 0.04° in a 1-dm. tube; a 0.5% soln. at 60° shows almost exactly the
same rotation; when the 1% warm aq. soln. is freed from its turbidity by repeated filtration about 0.3% remains in soln.
and shows [α] about 25°. Penta-m-digallyl-α-glucose, obtained in the same way from the Ac deriv. (yield, about 90%),
[α]D 18 41.3° (alc.), 44.6° (Me2CO); a warm 0.4% soln. becomes turbid when cooled to 25° and even a 0.2% soln. shows
a faint turbidity at 18°; after filtration it gives [α] about 51°. Hydrolysis in the same way of acetylated Chinese tannin
yields a product with ([α]D 18 24.4° (10% alc. soln.)20.95° (Me2CO), 71.4° (H2O); that obtained by alk. hydrolysis gives
40.3° in H2O. The pentagallylglucoses, previously obtained in purest state by hydrolysis of the Ac derivs. with NaOAc in
aq. Me2CO at 70°, protected from the air, are more conveniently obtained by the above method; the α-compd. shows
[α]D 16 60° in H2O, 81.5° in alc.; the β-compd., [α]D 18 15° and 24°, resp. Tannin may be purified through the K salt,
which is difficultly sol. in alc.; 50, cc. of a 5% alc. soln. of Chinese tannin is poured with continuous stirring into 50 cc. of
5% alc. KOAc; the colorless amorphous ppt., after washing with alc. and Et2O and drying in vacuo over P2O5, contains
some loosely held KOAc, [α]D 18 46.3°(1% soln. in H2O). Potassium pentadigallyl-α-glucose, [α]D 18 56.6°. β-Compound,
[α]D 18 33.7°. Potassium pentagallyl-β-glucose. All 4 of these salts contain almost exactly the same % of K (around
10.3%). Di[triacetylgallyl]ethyleneglycol, obtained in 10.1 g. yield from 12 g. (CH2OH)2, 15 g. triacetylgallyl chloride, 5.7
g. quinoline and 12 cc. CHCl3 allowed to stand 24 hrs. at room temp., lancet-shaped leaflets from Me2O-H2O, m. 172-3°;
6 g. in 75 cc. Me2CO treated in ice in the course of 10 min. with 80 cc. of N NaOH and allowed to stand 2 hrs. at 0° gives
2.6 g. of digallylethyleneglycol, microneedles. from aq. Me2CO, decomps. about 287° gives a deep blue color with alc.
FeCl3 and an abundant amorphous ppt. with not too dil. alc. KOAc; its tendency to cryst. is so great that moderately
concd. or colloidal aq. solns. cannot be prepd. and the mucilage test, which in this case is not characteristic anyhow,
offers difficulties; likewise, owing to its small soly. in alc. the H3AsO4 test for tannins cannot be applied to it. With C5H5N
and Ac2O it smoothly regenerates the Ac compd. It can also be obtained in 55% yield by heating 1 g. of the Ac compd.
in 5 cc. AcOH on the H2O bath 20 min. with 5 cc. of 5 N HCl Tri[triacetylgallyl]glycerol, obtained, in colorless, amorphous
form by pptn. from AcOEt with petr. ether, then rubbing with MeOH and H2O. Trigallylglycerol, faintly yellow-brown
amorphous brittle tanninlike mass, gives a deep blue soln. and blue-black ppt. with FeCl3, a heavy ppt. with mucilage,
also with C5H5N and aq. quinoline, quinine and brucine acetates and alc. KOAc; the 20% soln. solidifies on addition of an
equal vol. of 10% alc. H3AsO4 after a few sec. to a clear stiff jelly. Di[triacetylgallyl]trimethyleneglycol (7 g. from 1 g.
CH2(CH2OH)2, 9.5 g. triacetylgallyl chloride, 4.3 g. quinoline and 10 cc. CHCl3), lancet-shaped leaflets from AcOEt, m.
159-6o°. Digallyltrimethyleneglycol (0.5 g. from 1 g. of the Ac compd. in 2 cc. AcOH heated 10 min. at 90-5° with 4 cc. of
5 N HCl), elongated leaflets, m. about 270° (decompn.); owing to its slight soly. in H2O it gives no characteristic ppt. with
mucilage, but a 10% alc. soln. very quickly forms a jelly with an equal vol. of 10% alc. H3AsO4 and KOAc a copious ppt.
Tetra (triacetylgallyllerythritol (6 g. from 1 g. erythritol, 11 g. triacetylgallyl chloride, 5 g. quinoline and 10 cc. CHCl3),
needles from aq. Me2CO, sinters 165° to a transparent mass becoming dear at 185° and mobile a few degrees higher.
Tetragallyterythritol(1.4g.from3 g.of the Ac compd. with HCl in AcOH), druses from aq. Me2CO, turns brown 288°,
decomps. completely about 20° higher, gives a distinct pptn. when a warm dil. alc. soln. is quickly cooled and at once
treated with 1% mucilage; in pure H2O, owing to the slight soly., the reaction is not decisive. The alc. soln. is also too dil.
to give the H3AsO4 test but KOAc produces a distinct, though faint, ppt. Hexa[triacetylgallyl]mannitol, amorphous sticky
ppt. from AcOEt-petr. ether, converted into a solid faintly brown powder by rubbing with H2O, Hexagallylmannitol, from
the Ac compd. with alkali in aq. Me2CO at 0°, amorphous, faintly brown mass, [α]D 16 27.0°(alc.), gives a strong test in
H2O with FeCl3 and ppt. with mucilage and the usual alkaloid acetates, and in alc. a jelly with H3AsO4 and a ppt. with
KOAc. The change of tetraacetyl-βglucose into the α-compd. on standing in alc. is effected much more rapidly if C5HsN
is added and the soln. is boiled a short time. Thus, when 7 g. of the β-compd. in 70 cc. MeOH is boiled gently for 20 min.
with 0.6 g. C5H5N, evapd. in vacuo, freed from the last traces of MeOH by dissolving twice in 50 cc. C6H6 and evapg. in
vacuo, allowed to stand 24 hrs. with 8 g. triacetylgallyl chloride, 4 g. quitioline and 30 cc. CHCl3, there is obtained 8 g. 1-
[triacetylgallyl]tetraacetyl-a-glucose still containing considerable of the β-compd., yielding after crystn. from C6H6 and
AcOEt-petr. ether 3.2 g. of quite pure α-compd., slender microneedles, m. 158-90°, [α]D 18 99.90° in (CHCl2)2;
hydrolyzed with alc. NH3, pptd. with basic Pb acetate and purified by boiling out with AcOEt it yields an easily sol.
substance consisting chiefly of 1-gallyl-α-glucose which could not be obtained in cryst. form, rotates to the right, differs
from the β-compd. (glucogallin) in its greater soly. in H2O and alc. and on reacetylation gives the original hepta-Ac
compd. in large yield. 1-Benzoylletraacetyl-α-glucose, from 7 g. tetraacetyl-β-glucose rearranged into the α-compd. as
before described, freed from alc. by repeated evapn. with C6H6, allowed to stand 24 hrs. with 3 g. BzCl, 3 g. quinoline
and 15 cc. CHCl3, then dild. with sufficient CHCl3 to effect soln., washed carefully with H2SO4, NaHCO3 and H2O,
evapd., crystd. from 6 cc. alc. (whereby 7-7.5 g. of a mixt. of the α-and β-compds. seps.), extd. 15 min. with 5 parts Et2O
at-10° to-15°, evapd., made to cryst. by rubbing with a few drops alc. (2.8 g.), thoroughly rubbed with lo parts CCl4 (which
diminishes the yield 0.5) and finally crystal. from AcOEt-petr. ether, long needles, m. sometimes 60-30°, often 10-20°
lower, [α]D 18113.5° (CHCl3). 1-[p-Acetoxybeneoyl]tetraacetyl-β-glucose, obtained in 13.8 g. yield from 10 g. tetraacetyl-
β-glucose, 6.5 g. p-AcOC6H4COCl, 4.1 g. quinoline and 20 cc. CHCl3, long needles from Me2CO-H2O, m. 172-3°, [α]D 18
-30.6° in (CHCl2)2; its hydrolysis can be effected with 1 mol. of alc. NaOH, 5 g. in 50 cc. alc. treated with 1 cc. aq. 10 N
NaOH and then, in the course of 30 min. with 50 cc. of H2O in 5-cc, portions being completely hydrolyzed in 1 hr.; the alk.
liquid is treated with 15 g. Pb(OAc)2 in concd. aq. soln., then with small portions of concd. NH4OH until the ppt. no longer
increases and the latter is decompd. with H2S in 250 cc. H2O, dild. with 150 cc. alc., heated nearly to boiling, filtered,
SciFinder® Page 26
evapd. in vacuo to 20 cc. and kept at 0° for a short time; there is thus obtained 1.65 g. of I-P-hydroxybenzoyl-β-glucose,
flat needles, m. 228° (foaming), [α)D 17-23.9°lc.), strongly reduces hot Febling soln. If 5 g. of the penta-Ac compd. in 50
cc. alc. satd. at 0° with NH3 is kept 5 hrs. in a closed vessel at 0° and 1 hr. at 18°, evapd. in vacuo at about 30°, taken up
in 50 cc. H2O and treated with Pb(OAc)2 as above, there is obtained a mixt. of needles and a sirup which, when digested
with 30 cc. cold Me2CO, yields 1 g. of the hydroxybenzoylglucose, while the Me2CO ext. gives a small amt. of a
substance, m. 177-80°, which appears to be a monoacelate. If 5 g. of the pentaacetate is allowed to stand only 45 min.
with 50 cc. alc. satd. at 18° with NH3 and evapd. to dryness in vacuo there is obtained 3 g. of the tetraacetate, crystals
from EtOH-H2O with 1 H2O, m. 196-7°, [α]D 18-38.4° (Me2CO), strongly reduces Fehling soln. 1-[p-
Acetoxvbenzoyl]tetraacetyl-α-glucose, m. 134-5°, [α]D 18 116° (CCl4); treatment with alc. NaOH, Pb(OAc)2, etc., as for
the-β-compd. gives an exceedingly sol., strongly d-rotatory sirup, which reduces Fehling soln., easily forms
phenylglucosazone and contains much HOC6H4CO2H, but cannot be crystd. or reconverted into the pure pentaacetate. It
has been found that β-pentaacetylglucose (1.5 g.) can also be hydrolyzed completely (90%) in 35 cc. alc. by 2.3 cc. aq.
N/3 NaOH; glucose can be obtained in 50% yield from 5 g. of the pentaacetate in 100 cc. alc. and 12 cc. of 0.5 N NaOEt
after 24 hrs. Similarly α-methyl glucoside is obtained in 75% yield from 3.6 g. of the tetraacetate in 50 cc. alc. and 20 cc.
of 0.25 N NaOEt after 24 hrs. at 15°.
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35. Plastic mixtures

By Mooser-Schiess, W.
CAPLUS
Plastic materials are formed by mixing yeast with esters of polyvalent organic acids with polyvalent alcs. Suitable esters
are those of the dibasic aromatic acids, e. g., the glycerol esters of phthalic acid or naphthalic acid or glycerol esters of
the polyvalent cyclic series such as those of the camphane series may be employed. Acetylated derivs. of starch, sugar
or cellulose also may be used. Volatile organic solvents are used in forming the mixts. and the products may be shaped
as desired by rolling or subjection to hydraulic pressure. Fillers or substances increasing the flexibility of the product may
be included as additional ingredients, e. g., cellulose, resins, kieselguhr, mica or soap. Wet yeast containing alc. is
especially suitable for use with such substances as acetylated or nitrated cellulose derivs. as the alc. facilitates the
production of a uniform mixt. CH2O, (CH2)6N4 or other hardening agents may be added at the same time or after the
other ingredients are mixed. Examples of mixts. suitable for molding are: (a) dry yeast 1000, glycerol ester of phthalic
acid 100, chalk 40 parts; (b) wet yeast 1000, glycerol ester of naphthalic acid 200, glycerol 500 parts; (c) glycerol ester of
phthalic acid 50, dry yeast 10-40 and acetylated cellulose 100 parts (which forms a gum-like mass); dry yeast 1000,
glycerol ester of "camphor acid" 100 and chalk 40 parts.
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36. Note on a deposit in refined soy bean oil

By Brightman, R.
From Journal of the Society of Chemical Industry, London (1919), 38, 120-1T. Language: Unavailable, Database:
CAPLUS
In the refining of soy-bean oil by H2SO4 it was sometimes observed that the refined oil became cloudy through the
formation of a white deposit which prevented the oil from burning. An examn. of this deposit showed it to be acid to
methyl orange and phenolphthalein, titrations giving 5.39% of free H2SO4 and 13.3% of oleic acid. About 64% of the
deposit was sol. in petroleum ether; and hot alc. extd. a white substance showing 7% S, 94.3 sapon. no., I no. 120.5,
unsapon. matter 3.5 %, increase on acetylation 5.5 %. The fatty acids, obtained by sapon. of this substance gave
neutralization no. 298, I no. 123.4, mean mol. wt. 308, m. p. 25°, S, none. These figures indicate that the S in the
complex forming the deposit is eliminated on sapon.; and to reconcile the low sapon. no. with the neutralization no. of the
fatty acids it is necessary to assume that the two mols. of glyceride are condensed through the SO2, group, thus:-
SO2(O.CH2.CHOR.CH2OR)2. Such a complex would break up on sapon. into 2 mols. of the glycerol, several mols. of
fatty acids and H2SO4. The acidity of the deposit and its soly. in petroleum ether suggests the presence of
dihydroxystearic acid. The fatty acids obtained from the deposit were sol. in petroleum ether and m. at 27.5°. The
acetylated product of these acids m. at 29° and has a sapon. no. of 229 and mean mol. wt. 245, figures which point
clearly to the presence of hydroxylated fatty acids.
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37. Japanese peppermint

SciFinder® Page 27
By Shinozaki, Einosuke
From J. Chem. Ind. Japan (1919), 22, 349-82. Language: Unavailable, Database: CAPLUS
cf. C. A. 13, 1896. S. gives data on (a) the nature of chemically treated peppermint oil, (b) effect of the time of cutting,
condition of the soil and climate on the amts. and characters of the oil, and (c) the peppermint oil industry in Okayama
and Hiroshima provinces. The oil after sapon. and purification looks brownish yellow, has d25 0.8967, nD 25 1.4615, [α]D
25 37.48, solidifies at 20.7°. If combined menthol is changed to free menthol, and all ketones are redued, and then
sapond., the oil becomes much sweeter, having d25 0.8963, nD 25 1.4621, [α] -35.45, solidifies at 25.4° Acetylation
converts it to sweeter oil, which has greater d. and [α], less combined menthol, and which does not solidify. As to the
effect of the time of cutting, S. finds that the 2nd crop yields the greatest amt. of oil (2%), 3rd 1.5%, 1st 1.0%. The plant
raised on dry soil gives about 0.2% more oil than the wet, having also higher d., [α], ester no. (or combined menthol), but
lower n and acid no. than that from wet soil. Free and combined menthols are greater in amt. in the plant from dry soil in
the case of the Okayama, but the Hiroshima peppermint shows the reverse. The detailed method for com. prepn. of the
oil and industrial data from different markets are given.
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38. Transpositions in the camphene series. II

By Langlois, G.
From Annali di Chimica Applicata (1920), 12, 265-363. Language: Unavailable, Database: CAPLUS
SciFinder® Page 28
This second part consists of 9 chapters discussing the exptl. work of the study (cf. C. A. 14, 937). 1. The halogenation of
camphene: Bromocamphene (A) or camphenylidene-6-bromomethane is made by treating camphene in anhydrous Et2O
with Br. A HBr salt of A is formed from which A can be isolated by treating with PhNMe2. It b15, 115-20°; b. 225-6°; d.
1.265; αD + 68.85. The constitution of A was established by two methods of oxidation, one with HNO3 vapors and the
other with KMnO4, and by the transformation brought about by treatment with Mg, giving an ethylenic acid C10H15CO2H,
m. 122-4°. The Et2O soln. from this prepn. gave brilliant white crystals slightly sol. in Et2O and nearly insol. in alc. that
will sublime. They are sol. in CHCl3, m. 186°, giving a clear liquid. This is a polymer of the monovalent radical C10H15,
and is called dihydrodicamphene or dicamphenylidene-ethane. It is very hard to burn, is very stable and cannot be
oxidized by KMnO4. The C10H15CO2H is oxidized by KMnO4 to camphenylone and (CO2H)2. A is not oxidized by a
dichromate mixt., showing a very curious case of stabilizing an unstable mol. by substitution. HBr passed through A
forms dibromocamphene (B) or 2-bromo-Ω-bromocamphene, m. 90-1°. Semmler maintains that B is very stable. L.
proves that the reaction is a reversible one and thinks that it is of the enol type, but has not been able to demonstrate it
experimentally. Cl gas passed through A in Et2O formed a dichlorobromocamphene, m. 74°. A saturated with dry Hcl
gas at ordinary temp. is unchanged, showing a remarkable difference from the action of Hbr. Hcl gas passed through A
at 100° forms some dibromocamphene. Acetylation of A produced considerable resin with no definite product, while with
camphene, isobornyl acetate is formed. Chlorocamphene (C) or camphenylidene-6-chloromethane is more difficult to
prepare than A. Cl passed through camphene in Et2O gives a mixt. of unchanged camphene, C and the Hcl salt of
camphene. This mixt. heated with PhNMe2 gives camphene and a liquid C, b15, 95-8°, d15 1.016-1.017, αD + 37°. With
KMnO4 C forms camphenylone, identified by its semicarbazone, m. 223-4°. A dichromate acid mixt. will not affect C. Dry
Hcl on C forms neither a Hcl compd. nor a dichlorocamphene. HBr acting on C forms white crystals, sensitive to light, of
2-bromo-Ω-chlorocamphene, m. 103°. Cl gas passed through C forms trichlorocamphene, snow-like crystals, m. 104°.
Br passed through C in Et2O forms dibromochlorocamphene, perfectly white and very slightly sol. in alc., m. 64-5°. 2.
Method of synthesis of compds. of the camphene type: Camphene heated on an oil bath at 120° with AcOH and
trioxymethylene condenses to form all acetate of a primary alc. AcOC11H17, which can be hydrolyzed to the alc.
C11H17OH (D) with alc. KOH. Care must be taken to avoid the formation of the ether (C11H17)2O, b15, 235-40°, d20
0.983, during the hydrolysis. This alc. is purified by forming a phthalate with C6H4(CO)2O, very white crystals, m. 124-5°.
The alc. can be obtained from the phthalate by treatment with soda and distg. with steam; it b. 234-8°, has αD + 45°, d15
0.987-0.988, is a liquid, practically odorless, very like glycerol, uncrystallizable and sol. in the majority of org. solvents. D
with KMnO4 in presence of Na2CO3 produces camphenylone, which is identified by its semicarbazone. During this
oxidation oxycamphenylinic acid, m. 184°, is also prepd. Oxidation of the alc. with KMnO4 in a strongly basic soln. gives
camphene-camphoric acid, m. 135°. The ether oxide oxidized with a CrO3 mixt. gives an aldehyde of D, whose
semicarbazone m. 233°, and camphenylideneethanic acid, m. 124-5°. Brominating D gives a di-Br deriv. which is not
cryst. and cannot be distd. A diphenylurethan deriv. is made by treating D with Ph2NCOCl. An excess of pyruvic acid
and D give a pyruvic ether b10 150-5°, whose semicarbazone m. 167°. 3. The chloride of D: Dry Hcl passed through D in
PhMe gives the chloride C10H25CH2Cl, b15 110°, d15 1.020, and the sym. ether (C11H17)2O (E), b16 215°. PCl5 acting on
D produces the chloride as well as PCl5 on E. The chloride is a more mobile liquid than D and is sol. in org. solvents, αD
+ 27.38°. It is oxidized by KMnO4 to camphenylone. The chloride is not reduced when treated with metallic Na and abs.
alc. but a mixed ether is formed, C10H17OEt, b. 230°, d15 0.917. The same mixed ether is produced when NaOEt is
used. E is oxidized with a CrO3 mixt. to camphenylideneacetic acid and a little of the corresponding aldehyde. The
chloride of D reduced with Zn and Hcl forms methylcamphene, b. 178°, d15 0.888, αD, 4.28°. There is also some D
formed by hydrolysis. E left stand undergoes autoöxidation to camphenylideneacetic acid and the corresponding
aldehyde. By the Wurtz reaction using Na, two moles of the chloride of D will combine to form dicamphenylidenebutane,
b25 210°, d15 0.952, αD 67.30°. This compd. will add Br but a color that develops during the process makes it difficult to
know the amt. of Br required for satn. Mg and the chloride of D give exactly the same reaction that Na does, rather than
an acid of 12 C atoms as expected. The sym. oxide (C11H17)2O was prepd. by treating the sodium alcoholate of D with
the chloride. It b. 235°, d15 0.983. The cyanide of D, C10H15CH2CN, was made by treating the chloride with NaCN, b12
140°, d15 0.959, d20 0.963, αD 61.20°, easily oxidized by KMnO4 to camphenylone. The hydrolysis of the nitrile gives off
NH3 as usual but the acid formed is evidently a mixt. of isomeric acids, b24 185°, αD 41.16°, composed of the normal acid
(α), RCH2CO2H, and the abnormal one (β) R = CHCOOH. The latter will give by oxidation camphenylanic aldehyde. 4.
Camphenylidene-6-ethanal, C10H15CHO, is prepd. by oxidizing D with a dichromate acid mixt. and is always
accompanied with some acid production. The aldehyde is sol. in most org. solvents, b12 130°, b8 124°, d15 1.002, αD
72.58°, forms a fine cryst. bisulfite compd., undergoes autoöxidation to the acid, gives Schiff's test, but will not give the
Cannizzaro reaction and does form a semicarbazone m. 233°. Oxime b15 160°, from the aldehyde and NH2OH.Hcl,
forms a Hcl salt insol. in Et2O, when dry Hcl is passed through its soln. and this compd. cannot be crystd. The oxime
when dehydrated with Ac2O forms 2 mols. of AcOH and the nitrile C10H15CN, b6 132°, b15 140°, d15 0.987, d20 0.983, αD
+ 110°. The sapon. of this nitrile does not produce NH3, and an acid but does give a stable amide C10H15CONH2 by
simple addition of H2O. The aldehyde with Ac2O will not undergo enol formation but does form a diacetate, m. 54-5°. 5.
Camphenylidene-6 ethanic acid (F), C10H15CO2H; F, formed as the second stage of oxidation of D, big 181°, crysts. from
alc. or benzine in white brilliant crystals, m. 124-5°; heated on an oil bath several hrs. it loses CO2, forming camphene,
which is inactive. b. 158-60°, m. 45-6°, αD = 0°, oxidized by dichromate acid mixt. to dl-camphor m, 176-7°. This
camphor can be changed to an oxime with NH2OH, HCl and ZnO2 m. 120°. The ethyl ester of F, prepd. by treating F
with EtOH in H2SO4 soln., b2, 150°, d20 1.008. Oxidation of F with KMnO4 is a good method for prepg. pure
camphenylone. The acid chloride of F, from F with PCl5, b15 145°. Alc. KOH added to the chloride forms the K salt of F
easily. The acid chloride dropped into aq. NH4OH gives the cryst. acid amide, m. 192°, brilliant crystals, odorless, slightly
sol. in Et2O, sol. in 95% alc. F treated with AmOH and Na and heated gives a homolog of F, isocamphane-carboxylic
acid or homocamphenylanic acid, m. 75-6°. 6. Reduction of the C11 aldehyde by nascent H. Prepn. of Ω-
methylcamphene: The aldehyde is reduced by a Zn-Hg in dil. HCl to methylcamphene, b. 178°, d15 0.884, αD + 4°. The
oxidation of methylcamphene with dichromate gives camphenylone, (CO2H)2, oxycamphenylanic acid and camphene-
camphoric acid, the last two in very small quantities. Methylcamphene will not add Hcl gas to form a hydrochloride.
Acetylation with AcOH gives a small yield of the acetate, b10 120-30°. Dry Hbr produces a transposition in
methylcamphene to C11H18HBr, d15 1.175. 7. Synthesis of compds. of ketonic condensation to C14 and C15: The
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homoterpene aldehyde is treated with acetone and NaOEt, forming a ketone C14H20O, b12 160°, d15 0.980, a liquid sol. in
the usual org. solvents but it does not combine with NaHSO3. Its semicarbazone m. 220-1°. The same aldehyde with
MeOEt in presence of NaOEt gives a homolog C15H22O, an oil, sol. in the usual org. solvents, b12 172-5°, d15 0.968. It
does not form a bisulfite compd. and its semicarbazone m. 209-10°. 8. Synthesis of a series of diethylenic hydrocarbons
of the camphenic type with C12, C13, C14, and C15: The aldehyde C11 with Mg and MeI unites to form a hydrocarbon
C12H18 resembling metastyrolene, b10 85-90°, bn 203-5°, αD 76.39°, d15 0.921, d20 0.917. This hydrocarbon oxidized
with dichromate gives camphenylideneacetic acid, m. 124-5°. A little of the corresponding aldehyde is formed at the
same time, whose semicarbazone m. 233°. A hydrocarbon C13H20 is made in a similar manner using EtBr, b3 230-2°,
d15 0.919, αD, 700°. When it is oxidized with dichromate camphenylidene-acetic acid is produced as before as well as a
little of the corresponding aldehyde. A hydrocarbon C14H22 is prepd. in the same way, using PrBr, bn 238-40°, αD 80°,
d15 0.905. Its oxidation products with dichromate are the same as before. A synthetic sesquiterpene, sesquicamphene,
C15H24, is prepd. from the aldehyde with Mg and BuBr as a mobile, nearly odorless liquid, insol. in alc., d15, 0.900, bn
255°, αD 73.5°. Oxidation of C15H24 gives the same products as before. All these hydrocarbons can be completely
oxidized with KMnO4 to camphenylone, as camphenylideneacetic acid is only the first stage in their oxidation. 9.
Spontaneous oxidation phenomena: The ethoxycamphene compd. C10H15CH2OEt and the 4 hydrocarbons are all
oxidized spontaneously, giving a final residue of the acid C10H15CO2H and AcOH in the first case, with aldehydes from
the 4 hydrocarbons. The article is replete with equations and graphical formulas for all the reactions and compds.
discussed.
~0 Citings
39. The cocorice

By Pieraerts, J.
From Bulletin des Matieres Grasses de l'Institut Colonial de Marseille (1920), No. 3, 126-30. Language: Unavailable,
Database: CAPLUS
cf. C. A. 13, 2770. Cocorico is a variety of Citrullus vulgaris found in the Belgian Congo. The seed contains 37.5% of oil
having the following consts.: d15 0.9241, n20 1.4710, sapon. no. 196.3, I no. 113.9, R.-M. no. 1.3, glycerol 10.14%,
Hehner no. 93.68%, unsaponifiable matter 0.76%, sapon. no. of the acetylated oil 207.2. The oil has no drying
properties. The cake is suitable for fertilizer on account of its N content (6%). With the use of modern machinery and
methods it would be possible to produce this oil commercially.
~0 Citings
40. Proso millet investigations-analysis of the oil-a characteristic alcohol

By Dunbar, B. A.; Binnewies, E. R.
DOI:10.1021/ja01448a032
Proso millet (Panicum miliacum) is extensively cultivated in the region of the Altai Mts. in Siberia, in Southern Russia and
in the semi-arid areas of eastern and southern Asia, where it constitutes a stable foodstuff for man and the lower
animals. The present investigation was carried out on grain grown on the farms of the South Dakota College of
Agriculture and Mechanic Arts. Analyses on the hulled grain ground to pass through a 70-mesh sieve and on the same
grain, hulled, pulverized and bolted through a No. 60 mill screen, gave the following results, resp.: Ash 2.86, 1.45;
moisture 12.80, 10.09; crude fiber 6.25, 0.80; crude protein 15.86, 14-90; Et2O ext. 5.07, 3.32; N-free 57.16. 69.44;
starch 59.65, 69.15. The oil was obtained by extg. the meal (passed through a 40-mesh sieve) 16 hrs. with pert. ether; it
is of a medium straw color changing on standing to a light golden yellow and depositing peculiar crystals (see below). It
is a semi-drying oil, d22.5, 0.9228, n 1.4745, insol. in 95% alc. up to 35 vols. and in abs. alc. up to 25 vols., sapon. value
181.5, 1 no. (Hubl) 92.3, free fatty acids 119 mg. oleic acid per g., Ac value 39.23 mg. KOH per g., Reichert-Meissl value
2.5, unsaponiflable matter (Allen and Thompson) 2.52 % by wt. (in the main, resins), elaidin test (Andes) a foamy
orange-yellow buttery mass becoming red-brown and semi-liquid after 2 hrs., O absorbed (Livache) in 21 hrs. 3.18 %,
crude glycerol (Lewkowitsch) 3.31%, phytosterol (A. O. A. C. method) 0.63%, phenol tests negative, Schiff aldehyde test
very faint, mean mol. wt. of the fatty acids 296, volatile acids 0.36% (calcd. as HCO2H; a small amt. of AcOH is also
present), satd. acids 89.8% (sapon. value 195.9, 1 no. 96.6. mean mol. wt. 286), unsatd. acids (I no. 124, mean mol. wt.
314). The satd. acids consist chiefly of palmitic (approx. 80%), carnaubic and daturic, the unsatd. acids of oleic (51.6%),
linolic (20.4%) and an isolinolic acid (23.7%). The crystals sepg. from the oil (see above) sep. from 95 % alc. in 6-sided
pearly plates, m. 279° (cor.), give negative tests for aldehyde, acid, carbohydrate, phenol, ester, anhydride, lactone or
ketone groupings (except a slight test for ketones with NH2OH) but a positive acetylation test for an alc. grouping; they
contain 80.8% C and 10.1% H, mol. wt. in CHCl3 (Liebig method) 356, in CS2 (Menzies vapor density method) 369. D.
and B. conclude the substance has the mol. formula C24H36O2. With 1 cc. Ac2O and 2 drops concd. H2SO4 it gives a
purple color rapidly deepening to wine-red. This alcohol-ketone, in several respects allied to the phytosterols, is
provisionally designated as prosol.
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~0 Citings
41. Synthesis of fatty acid derivatives of the sugars. I

By Hess, Kurt; Messmer, Ernst
SciFinder® Page 31
Recently (C. A. 15, 1619) there was developed a view of the structure of cellulose which involved two new principles: (1)
It was shown that it is very probable that the glucose mols. are united in a "tannin-like" structure; e. g. each of the five HO
groups of one glucose mol. is joined in an ether union with another glucose mol., a view which presupposes a similar
ability of all the sugar HO groups to condense with long C chains. (2) To explain the production of cellulose with its high
mol. wt. it was assumed that these tannin-like structural elements (cellulose) combine through residual affinities
according to well defined laws. The development of the cellulose theory led away for the first time from the chain theory
for natural substances of high mol. wt. to a comb-like or more or less spherical structure for cellulose, starch and protein.
This theory also brings the structure of cellulose nearer to that of the fats, in which there is a massive accumulation of
fatty acid chains through the instrumentality of glycerol. The cellulose theory permits of attacking the problem of the
structure of cellulose in two ways; by the analytical degradation of cellulose according to the above points of view (more
on this will be published elsewhere), and by the synthesis of analogs of cellulose; these synthetic analogs might make it
possible to discover properties which are related to those of cellulose, such as soly. in CuO-NH4OH, swelling in neutral
salts, etc. In this connection it was of especial importance to establish any possible differentiation in the ability to
condense of the five HO groups of the glucose mol. Fischer showed that in the esterification of glucose with aromatic
HO acids all five of the HO groups of glucose have the same ability to condense, but this might be entirely different with
aliphatic chains, especially the longer ones. Although the acetylation of sugars by various methods has come to be an
important process in sugar chemistry the reaction has thus far not been extended to the homologs of AcOH. H. and M.,
having found that acetylation can be smoothly effected with AcCl at -15° with formation of α-pentaacetylglucose, tried
higher acid chlorides and obtained pentaacyl derivs. and also obtained compds. of the same compn. by an extension of
the reaction of Behrend and Roth (Ann. 331, 362(1904)), viz. acetylation with Ac2O in the presence of C5H5N, to
homologous anhydrides. While the optical rotation of the products obtained from the anhydrides indicated that these
products were the α-isomers and AcCl, as stated above, also gave the α-compd., the rotations of the compds. obtained
from the other acid chlorides not only differed from those obtained from the anhydrides but also from those of the β-forms
(which were also prepd.) so that the compds. prepd. from the chlorides are possibly structural isomers derived from
another than the γ-oxide form of glucose. The pentapalmityl-, pentastearyl- and pentaoleylglucoses, octapalmityl- and
octastearylsaccharoses and hendecapalmityl- and hendecastearylraffinoses have the properties of ordinary glycerol fats
and H. and M. believe it is quite possible that there exist in nature fats in which the alc. constituent is a sugar instead of
glycerol and that such fats may have already been discovered but not recognized as such; in the future it might be
advisable to det. whether natural fats, under the conditions described below, attack Fehling soln. and, if so, to search for
the sugar constituents; cf. in this connection Taylor and Nelson, C. A. 14, 2942. In spite of the increased mol. wt. the m.
ps. of these sugar fats are not higher, as compared with those of the corresponding free fatty acids, than those of the
glycerol fats. The sp. rotation of the products prepd. from the acid anhydrides decreases, apparently according to a
definite law, with increasing mol. wt. This regular decrease confirms the view, expressed above, that all these compds.
belong to the α series. If the same regular decrease holds for the β-series, it is quite conceivable that the rotation of
cellulose, which is made up exclusively of β-glucose mols., might become so small as to fall within the limits of the exptl.
error and thus explain its apparent optical inactivity. By assuming a similar ability of NH2 acids to condense with sugars,
the high mol. wt. of proteins can be simply explained without the assumption of giant chains. α-Pentaacetylglucose, m.
111-2°, is obtained in 3-g. yield from 1.8 g. anhydrous glucose suspended in 10 cc. C5H5N (distd. over KOH) and 5 cc.
CHCl3 (distd. over P2O5) treated very slowly at -10° to 15° with 4.3 g. AcCl in 5 cc. CHCl3, allowed to stand 1-2 hrs. in a
freezing mixt., then slowly allowed to rise to room temp. (15-8°), dild. after 2-3 days with 30 cc. H2O, treated with N
H2SO4, extd. with Et2O, carefully freed from C5H5N, then from AcOH with N NaOH, washed with H2O and dried over
KOH. If quinoline is used instead of C5H5N, evapn. of the Et2O gives an α-pentaacetylglucosequinoline addition product,
C25H29O11N, as a clear honey-yellow sirup forming on contact with H2O a crumbly powder, which, desiccator-dried,
contains 0.5 mol. H2O. In the same way from 1.8 g. glucose in 10 cc. each of C5H5N and CHCl3 and 5.9 g. EtCOCl in 5
cc. CHCl3 is obtained 3.1 g. pentapropionylisoglucose, b1 193-5°, [α]D 16 80.87° (CHCl3), quickly reduces boiling Fehling
soln. The normal α-pentapropionylglucose, obtained from 1.8 g. glucose allowed to stand 5 days'at room temp. with 8.9
g. (EtCO)2O and 10 g. C5H5N, concd. in vacuo, treated with 30 cc. N H2SO4 and extd. with 50 cc. Et2O, b2 205°, [α]D 16
6l.06°. Pentabutyrylisoglucose (3.1 g. from 1.8 g. glucose and 5.8 g. PrCOCl), b2 240°, b2 215-20°, [α]D 16 73.31. α-
Pentabutyrylglucose (4 g. from 1.8 g. glucose and 11.2 g. (PrCO)2O), b1.5 228-30°, thick, almost odorless oil, [α]D 16
52.04°. Pentaisovalerylisoglucose (4.3 g. from 1.8 g. glucose and 6.5 g. iso-BuCOCl), b2 242°, solidifying to long
needles, m. about 43°, easily sol. in all solvents and can be crystd. Only by adding H2O to an alc. soln. to incipient
turbidity and allowing to cool, [α]D 16 15.19°. α-Pentaisovalerylglucose, b2 242°, [α]D 16 43.68°. α-Pentacapronylglucose,
from glucose with AmCOCl or (AMCO)2O, b0.01 240-5°, [α]D 16 44.28-44.48°, reduces Fehling soln. after short boiling with
aq. alc. alkali. α-Pentapalmitylglucose, obtained in good yield from 1.8 g, glucose in 20 cc. C5H5N at-10° treated with 14
g., palmityl chloride in 20 cc. CHCl3, allowed to stand some hrs. at this temp., gradually raised to room temp., and treated
with 20 cc. CHCl3 to assist in redissolving the cryst. mass which is deposited (probably an addition product of the
chloride and C5H5N), gently warmed several hrs. on the H2O bath, allowed to stand overnight, filtered and crystd. from
alc., seps. in snow-white aggregates of microcrystals and after drying over H2SO4 forms a friable but soft mass, m. 65-7°,
[α]D 16 34.30°, reduces Fehling soln. after short boiling in alc. with a few drops of 2 N NaOH, has the same solubilities as
tripalmitin, is wholly tasteless; that it is the α-form is indicated by its position on the rotation curve although the synthesis
from the anhydride has not been carried out. α-Pentastearylglucose (4.5 g. from 0.9 g. glucose and 10.5 g. stearyl
chloride), flocculent, apparently cryst. mass from alc., m. 70-1°, [α]D 16 34.17°, is tasteless and behaves towards solvents
and Fehling soln. like the preceding compd. β-Monostearyltetraacetylglucose, from 1.05 g. β-acetobromoglucose in 20
cc. xylene gently warmed on the H2O bath with 0.95 g. Ag stearate, evapd. in vacuo, taken up in Et2O, freed from any
stearic acid with dil. NaOH, evapd. and crystd. from ligroin, rosets, m. 78°. α-Pentaoleylglucose (7 g. from 1.8 g. glucose
in 20 cc. C5H5N and 10 cc. CHCl3 treated with 15.1 g. oleyl chloride in 10 cc. CHCl3, allowed to warm up to 15-8°, treated
with 10 cc. CHCl3, heated several hrs. under a reflux on the H2O bath, cooled, decanted from the oil which seps., evapd.
in vacuo, taken up in H2O and Et2O, freed from C5H5N with dil. H2SO4, treated with NaCl to break up the emulsion,
washed with dil. NaOH, dried with K2CO3, evapd., taken up in Et2O, freed from the last traces of Na oleate by pptn. with
petr. ether, evapd. and washed several times with hot abs. alc.), is a brownish, relatively mobile oil, reduces Fehling soln.
after boiling with aq. alc. alkali, cannot be distd. under 2-3 mm., [α]D 16 27.51°. Octapalmitylsaccharose (5-6 g. from 1.8
SciFinder® Page 32
g. cane sugar and 12 g. palmityl chloride), pptd. from petr. ether with alc. as a soft granular mass, m. 54-5°, [α]D 16
l7.12°. Octastearylsaccharose (14 g. from 1.8 g. cane sugar and 17 g. stearyl chloride), spherical microgranules from
CHCl3-EtOH, m. 57°, [α]D 16 16.55°, shows the same solubilities as the preceding compds. and the glycerol fats, reduces
Fehling soln. after alk. hydrolysis and inversion with acids. Hendecapalmitylraffinose (12.6 g. from 0.5623 g. anhydrous
raffinose and 30.2 g. palmityl chloride), pptd. from petr. ether-Et2O by EtOH as a yellowish fat-like mass with fatty taste,
softens 39°, m. 43°, can be pressed to a waxy mass, [α]D 16 4.15°. Hendecastearylraffinose, m. 63°; by working
exclusively at room temp., after initial cooling, were obtained products containing a higher rotating isomer, [α]D 16 27.17°
(m. 47°), and 10.02°. Pentahippurylglucose (5.9 g. from 6.3 g. hippuryl chloride in 20 cc. CHCl3 and 1.16 g. glucose in
10 cc. C5H5N and 9 cc. CHCl3 allowed to stand 4 hrs. at -15°, then 1-2 days at room temp., evapd. in vacuo at 35°,
shaken several times with dil. H2SO4 and Et2O whereby most of the product was deposited on the walls of the funnel as
a somewhat resinous mass, repeatedly washed with H2O and dil. alkali, taken up in alc., evapd. in vacuo over H2SO4,
pptd. from alc. by Et2O and rubbed with H2O), forms a yellowish powder with 2H2O (desiccator-dried), [α]D 16 9.8°.
~0 Citings
42. Glucosides. IX
By Karrer, P.; et al.
From Helvetica Chimica Acta (1921), 4, 130-48. Language: Unavailable, Database: CAPLUS,
DOI:10.1002/hlca.19210040110
K has shown (C. A. 13, 1841; 14, 742, 1972) that BrC6H7O5Ac4 (A) reacts with the Ag salts of α- or o-HO and o-NH2
acids to form both acetylated glucosides and glucose esters, indicating that the Ag is bound to both the CO2H and the
OH or NH2 groups by principal and secondary valences. On this assumption, m- and p-HOC6H4CO2Ag should yield
tetraacetylglucose esters but no glucoside, since the more distant OH groups would exercize no appreciable effect on the
Ag atom. By boiling 25 g. of p-HOC6H4CO2Ag with 41 g. of A in 200 cc. of C7H8 for 1.5 mins. and filtering while hot
tetracetylglucose p-hydroxybenzoate crystd. from the filtrate on cooling, m. 197°, [α]D 20 -29.76°. On extg. the filtrate with
dil. NH3 and acidifying, a white cryst. ppt. was formed, identical with the above compd. No glucoside was found.
Similarly, tetraacetylglucose m-hydroxybenzoate was prepd., white needles from EtOH, m. 147°, [α]D 20 -26.61°. The
combination between Ag and S in HSCH2CO2Ag was apparently too firm, as no reaction with A took place. Instead of
using the Ag salt, 17 g. of A in 25 cc. of abs. MeOH were mixed with 2 g. of K in 25 cc. of MeOH, to which 7 g. of
HSCH2CO2Et had been added. KBr was pptd. and removed after 2 hrs. and the filtrate evapd. in vacuo at 30-40° to
remove MeOH. The resinous residue was digested with Ac2O and AcONa to restore any Ac group split off, treated with
cold H2O to destroy Ac2O, dissolved in Et2O, the soln. evapd., and the crude product extd. with hot H2O. On cooling,
long needles of ethyl β-tetraacetyl-d-glucosidoothioglycolate formed, sol. in EtOH, Et2O, C6H6, m. 63°, [α]D 15 -58.52°.
Satd. Ba(OH)2 converted it into β-d-glucosidothioglycolic acid, m. 148-50°, [α]D -66.19°. From 20 g. of 2,5-
HO(MeO)C6H3CO2Ag and 30 g. of A in 250 cc. of boiling C7H8, AgBr was pptd. and removed, and the C7H8 soln. extd.
repeatedly with 50-cc. portions of 1:40 NH3. The latter was acidified with HCl, after filtering, giving a white cryst. ppt. of
β-tetracetyl-d-glucosido-5-methoxygentisinic acid (B), needles from EtOH, m. 172-4°, [α]D 20 -32.13°. From the C7H8
after the NH3 extns. tetracetylglucose 5-methoxygentisinate crystd. on evapn., needles from EtOH, m. 163°, [α]D 20 -
40.2°. Cold satd. Ba(OH)2 sapond. B of β-d-glucosido-5-methoxygentisinic acid (C), fine needles from EtOH, m. 166°,
[α]D 20 -39.62°, easily sol. in H2O, insol. in Et2O. Methyl ester of C, by the action of CH2N2 in Et2O on C in concd. EtOH
soln., m. 83°, [α]D 20 -48.52°. The above method applied to 13 g. of Ag p-methylmandelate and 25 g. of A in 125 g. of
C7H8 gave 16 g. of dl-tetraacetylglucose p-methylmandelate, snow-white needles, m. 155°, while the NH3 extns. yielded
5 g. of β-d-tetraacetylglucosido-p-methylmandelic acid, small felt-like needles, m. 149-50°. By the action of KCN and
concd. HCl on 50 g. of o-ClC6H4CHO at 0°, 55 g. of o-chlorobenzaldehyde cyanohydrin were obtained, and converted
into o-chloromandelic acid by sapong. with concd. HCl. Unchanged aldehyde was sepd. by extg. the crude product with
10% NaOH, acidifying and crystg. the acid from C6H6, the yield being 18 g., m. 84-5°. The acid was dissolved in EtOH,
treated with the equiv. amt. of AgNO3 in H2O, and NH4OH added from a buret, giving silver o-chloromandelate. From
15.6 g. of the latter, rubbed in a mortar with A and heated with 100 cc. of C7H8, AgBr was pptd. and removed, and the
C7H8 soln. extd. with 0.5% NH4OH as above, etc., giving β-d-tetraacetylglucosido-o-chloromandelic acid, small white
needles from dil. EtOH, m. 182°. Similarly, 8 g. of Ag orsellinate with the equiv. amt. of A gave tetraacetylglucose
orsellinate, m. 153°, [α]D 18 -41.75°. Ag quinolcarboxylate (Ag gentisinate) and A yielded tetraacetylglucose
quinolcarboxylate, white needles from EtOH, m. 185°, [α]18 -39.82°. Five g. of Ag mandelate and 13.5 g. of
acetobromomaltose in 100 cc. of boiling C7H8 gave a small yield of heptaacetylmaltosido-dl-mondelic acid, which could
not be obtained cryst., m. 65-85°, insol. in H2O, easily sol. in EtOH. Polarization in CHCl3 gave varying results, [α]D 9-
35°. This compd. agrees rather closely with acetylamygdalic acid in m. p. and [α], but is entirely different from
acetylcellosidomandelic acid, which is cryst., m., 179-82°, [α]D -44°. These facts furnish additional evidence that the
sugar of amygdalin is not a cellobiose, but is probably maltose or isomaltose. A study of the influence of various salts,
etc., on the rotation of glucosides showed that in 2% soln. salicin was affected by H3BO3, Na2B4O7 and NaOH, but not by
NaCl, KCl, KHC2O4, KNO3, CaCl2, or H2C2O4. Amygdalin was affected by Na2B4O7, which caused mutarotation, and by
NaOH. Menthyl α-glucoside was not affected by any of the above in 0.5% EtOH soln. or in 0.5% glycerol soln.
~2 Citings

SciFinder® Page 33
43. Mafurra tallow, a product of the nuts of Trichilia emetica
By Rindl, M.
From South African Journal of Industries (1922), 5, 415-23. Language: Unavailable, Database: CAPLUS
Both the husk and the kernel of mafurra nuts from Portuguese East Africa furnish a solid fat, while an oil is obtained from
the aril. The aril oil has the following characters: d15 0.931, acid value (as oleic acid) 8.9%, sapon. value 202.5, I value
66, sapon. value of acetylated oil 235. The oil congeals if kept for some time at about 5°. The consts. of the solid fat
obtained from different sources vary so widely that it is certain that all the com, material is not derived from the same
species of Trichilia. The kernal usually contains about 60% of fat, and the husk 25-35%. It has a high m. p., ranging
usually from 35-45°, and yields 7-8% of its wt. of glycerol on sapon. It has a notably high acid value (40-50).
~0 Citings
44. Investigations in the field of the olefin-magnesium compounds. I, II, III

By Krestinsky, W.
From Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen (1922), 55B, 2754-62,2762-
70,2770-4. Language: Unavailable, Database: CAPLUS
SciFinder® Page 34
In syntheses with the aid of Mg org. compds., halogenated olefins of the type CH2: CHBr, in which the same C atom
bears the halogen and the double bond, have thus far hardly been used at all, probably because of the general belief that
such halides do not react at all or do not react normally with Mg. The object of the present work was to fill in the gap
existing between the Mg compds. of satd. alkyl halides and those of C2H2 derivs. Action of Mg on isocrotyl bromide.
Me2C:CHBr (A) dild. with Et2O does not react with Mg under the usual conditions and only sluggishly and incompletely
on warming or addn. of I, but if the Mg is first activated with I according to Baeyer, then covered, still warm, with dry Et2O
and treated with the A in Et2O, the reaction begins generally spontaneously, otherwise on gentle heating, and then
proceeds so vigorously that occasional cooling becomes necessary. It is best, as soon as the reaction begins, to
immerse the flask in a bath at 18-20°, for if the temp. rises markedly there begins an intense evolution of gas and the Mg
org. complex apparently decomps. in part; on the other hand, if the temp. is kept too low, the reaction may stop. The
app. should be provided with an efficient stirrer and a Hg seal and the A added slowly to avoid local superheating. A
considerable portion of the Mg does not react; at the end of the reaction the contents of the flask consisted of a dark soln.
which on warming began to evolve gas again. As the end point of the reaction was taken the moment when the reaction
mixt., without being warmed, stopped boiling of itself. The evolved gas absorbed Br eagerly and decolorized KMnO4 but
did not react with Béhal's reagent or NH3-CuCl and gave no ppt. with HgCl2; its bromide chiefly b24 54-6°, b. 149-51°, d4
20 1.7827, n 1.51406, 1.51186 at 15° and 20°, and is apparently α,β-dibromoisobutane; the higher boiling fraction, b
D 19
107-9°, seems to be a tribromoisobutane; there were no indications of the presence of tetrabromides C4H6Br4. The gas
must therefore be Me2C: CH2 (B), formed according to the scheme: Me2C: CHMgBr → Me2C:C = or -CH2CMe:CH- +
HMgBr (1); Me2C:CHBr + HMgBr = Me2C: CH2 + MgBr2 (2). To det. the fate of the bivalent radical formed according to
(1) 213 g. A was treated with 29 g. Mg and 5 g. I; this gave 25 l. B, 30 g. unchanged A, about 15 g. of a product (C) b.
131-4°, free from halogen but contg. 10.450% O, and a fraction whose b. p. rose continuously. By means of a freezing
mixt. C was sepd. into a substance f. -23° and m. -12° and another which froze only in solid CO2. The former still
contained O (8.62%), reduced NH3-Ag2O with mirror formation, colored fuchsin-SO2, apparently did not react with
H2NCONHNH2, decolorized Br with explosive violence, reacted with EtMgI with distinct evolution of heat. The radical
Me2C: C =, therefore, must have reacted in some way with the Et2O, possibly with formation of an addn. compd. of the
oxonium type. Action of AcH on Me2C:CHMgBr; synthesis of methylisocrotylcarbinol (D). From 195 g. A, 37 g. Mg and
100 g. AcH were obtained 0.8 l. B and, after decompg. with H2O and refluxing about 7 hrs. with aq. KOH to remove any
unchanged AcH, 71 g. of a crude product yielding 12 g. EtOH, 20 g. D, 9 g. of a fraction (E) b. 185-205°, and 4 g. of a
fraction b. 228-32°. D has a pleasant alc. odor, decolorizes Br and KMnO4, d4 20 0.8384, n 1.43159, 1.43430, 1.44098,
1.44721 for C, D, F and G at 20°; 4 g. heated 20 hrs. at 100° in a sealed tube with Ac2O gives 3 g. of a mixt. of a
hydrocarbon, apparently α,α-dimethylerythrene (δ-methyl-α,γ-pentadiene), b. 75.5-6.0°, d4 20 0.72155, nD 20 1.44664,
and of the acetate of D, b. 140-6°. E on fractionation under 15 mm. is sepd. into 2 substances, apparently isomeric
alcohols C10H18O; one b15 80-7°, d4 20 0.8596, nD 20 1.55344, and the other b16 87-97°, d4 20 0.8763, nD 20 1.45854.
Synthesis and transformations of isopropylisocrotylcarbinol (F). From 165 g. A, 29 g. Mg and 88 g. Me2CHCHO were
obtained 8 g. iso-BuOH, 22 g. F and 13 g. of higher boiling fractions (175-220°). F b. 161-3°, d4 20 0.8444,nD 20 1.44493,
has a peculiar pleasant odor, decolorizes Br; 7.5 g. heated 30 hrs. at 100° with Ac2O gives 1.5 g. of the acetate, b. 177-
80°, d4 20 0.8270, n20 D l.43288, and 2 g. β,ε-dimethyl-α,γ-hexadiene (β-methyl-δ- isopropylerythrene) (G), b. 116-8°, d4
20 0.7412, n 20 1.45024, does not solidify -80°, gives with KMnO a little Me CO, a small amt. of a cryst. erythritol,
D 4 2
HCO2H, AcOH and Me2CHCO2H. F with KMnO4 yields Me2CO, two substances C8H12O3 (apparently stereoisomeric
α,α-dimethyl-α'-isopropylglycerols; one, difficultly sol. in Et2O, m. 159-60; the other, easily sol. in Et2O, very hygroscopic,
m. 73-5°), HCO2H, AcOH, Me2CHCO2H and a non-volatile acid forming a cryst. semicarbazone and a calcium salt, the
compn. of which, (C5H7O3)2Ca.H2O, indicates that the acid is dimethylpyruvic or isobutyrylformic acid. The formation of
G from F is most plausibly explained by assuming that the Ac2O not only acetylates the HO group of the F but that 1 mol.
AcOH simultaneously adds at the double bond and then splits off in a different way. As a matter of fact, when larger
amts. of F (25 g.) are treated with Ac2O, there are obtained, besides 7 g. G and a small amt. of a substance b. 224-7°,
two isomeric acetates of F: 2 g. b. 167-70°, d4 20 0.88676, nD 20 1.43739, and 5 g. b. 174-6°, d4 20 0.88226, nD 20
1.43238. Sapon. of the first with Ba(OH)2 gives an alcohol b. 158-61°, d4 20 0.8449, nD 20 1.43679, and the second
yielded an alcohol b. 160-5°, d4 20 0.8455, nD 20 1.43789. Dehydration of F with Al2O3. Passed over Al2O3 at incipient
redness, F gives chiefly diisocrotyl, Me2C:CHCHC:CMe2, b. 132-8°, solidifies in ice-salt (dibromide, m. 65°), and a
compd., probably α,α-dimethyl-γ-isopropylallene (β,ε-dimethyl-β,γ-hexadiene), b. 119-23°, solidifies at -80° but not at-23°,
d4 20 0.7637, nd 20 1.45054. Synthesis of phenylisocrotylcarbinol (H). H, from A, Mg and BzH, liquid of a strong, peculiar
odor, b7 122-5°, d4 20 0.9861, nD 20 1.53516. Action of Mg on β-methyl-γ-bromo-β-butylene (α,β,β-trimethylvinyl bromide,
"α-methylisocrotyl bromide") (I). I reacts with Mg like A, although not quite so readily. Thus, 200 g. I, 30 g. Mg and 5 g. I,
the Et2O distillate being subsequently treated with Br, give 146 g. Me2CBrCHBrMe, b17 61-5°. With HI gas instead of Br
the distillate gives EtI and Me2CEtI, and with Na does not react after 10 hrs. at 100° and 4 hrs. at 160-70°. The residue
remaining after distg. the Et2O, decompd. with cold H2O and distd. with steam, leaves behind 55 g. of material sepd. by
repeated fractionation into a fraction b. 120-5°, with 35.03% Br; one (chief fraction) b. 141-4°, with 70.68% C, 11.99% H,
mol. wt. in boiling C6H6 133; and a 3rd, b16 91-6°, with 80.46% C, 12.06% H. All 3 fractions are unsatd., have a pleasant
odor and contain O. Action of AcH on α-methylisocrotylmagnesium bromide. The product is apparently methyl[α,β-
dimetlzyl-α-propenyl]carbinol, an alc. of a very pleasant odor. Action of Mg on vinyl bromide. Preliminary expts. show
the reaction begins very quickly with evolution of C2H2 and C2H4.
~0 Citings
45. A new depolymerization product of starch

By Pictet, Ame; Jahn, R.
From Helvetica Chimica Acta (1922), 5, 640-5. Language: Unavailable, Database: CAPLUS
SciFinder® Page 35
The isolation of a new trihexosan indicates that starch is an aggregate of links composed of 3 hexose groups, rather than
a polymer of an anhydride of maltose. By heating potato starch in 10 parts of glycerol at 200-10° until the soln. just fails
to give a color with I (about 45 min.) and then quickly removing the solvent by vacuum distn. at the same temp. P. and J.
obtain a transparent vitreous, light brown solid. Soln. in H2O and pptn. with EtOH gives a white, amorphous slightly
hygroscopic powder (90% of the original wt.), trihexosan, (C6H10O5)3 (A), not identical with triamylose (cf. Pringsheim, C.
A. 8, 118; Karrer, C. A. 16, 1746) or isotriamylose, sol. in pyridine, insol. in HOAc and the usual solvents, decomps.
without m. 230-2°, mol. wt. 503, [α]D 25 162.2° (H2O), does not taste sweet, does not reduce Febling soln., is not pptd. by
I-KI soln. Hydrolysis with H2SO4 yields glucose (osazone m. 204°). A acetylated with 7 pts. Ac2O, yields trihexosan
nonoacetate (C6H7O5Ac3)3, colorless amorphous powder, from EtOH, sol. in Me2CO, HOAc, C6H6, pyridine, EtOH and
MeOH, insol, in H2O, Et2O and petrolic ether, m. 153-4°, decomps. 270°, mol. wt. 871, [α]D 26 125.9° (HOAc).
~1 Citing
46. The preparation of tuberculin

By Kresling, K. I.
From (Russ.) Arch. Biol. Sci. (1923), 23, 71-85. Language: Unavailable, Database: CAPLUS
The chief modifications of the old Koch method consist of substituting beef infusion broth for veal broth or meat ext.
bouillon in the mediums, the other constituents being 5% glycerol, 1% Witte peptone and 0.5% NaCl. The cultures were
permitted to grow for 5 to 7 months at 37°, during which period they were gently shaken up once or twice. The total
length of the growth period was standardized by estg. the bacterial mass and the amt. of unutilized glycerol. For the
detn. of the glycerol the acetylation method is especially recommended. K. also shows that growth of tubercle bacilli can
continue for much longer periods than the previously accepted period of 6-8 weeks, if the surface film on the cultures be
partially shaken down from time to time. The tuberculin obtained is claimed to possess very low toxicity and higher
immunizing properties.
~0 Citings
47. Chemistry of starch. X. Different construction of the two constituents of starch

By Pringsheim, Hans; Wolfsohn, Kurt
Both by acetylation with H2SO4 as catalyst and by heating with glycerol at 200-10° (Pictet and Jahn, C. A. 17, 270), P.
and W. have depolymerized amylose (I) and amylopectin (II), sepd. from each other by the method of Ling and Nanji (C.
A. 18, 79), into a disaccharide and a trisaccharide, resp., confirming the view already expressed that the basic unit of I
must contain at least 2, that of II at least 3 dextrose residues in glucosidic union. The I was obtained in 14% yield from
5% starch paste allowed to stand 12 hrs. at -10°, filtered at 60° from the cottony mass of II, concd. in vacuo and pptd.
with alc. The II was freed from the last traces of I by 12 hrs.' treatment with malt amylase at room temp. and
centrifugalization. The I and II were dried by repeated immersion in alc. to avoid their becoming horny. To 5 g. of the I or
II under 25 cc. Ac2O was added 1 cc. H2SO4 in 5 cc. cold Ac2O and the mixt. heated to boiling, cooled and poured upon
ice. II gave an acetate C36H48O24, mol. wt. in PhOH 899-913, [α]D 20 143.6-4.2° in (CHCl2)2, and I an acetate C24H32O6,
mol. wt. in PhOH 501-53, [α]D 20 142.4-2.8° in (CHCl2)2. From 2.0 g. II in 25 cc. glycerol gradually heated to 200-10° and
kept at this temp. until a sample gives a burgundy-red color with I (about 1 hr.) is obtained a trihexosan, mol. wt. in H2O
506-10, [α]D 2O 165.2-5.7° (H2O), while I (3-4 drops of 20% H3PO4 must be added to the glycerol) gives a dihexosan,
mol. wt. 299-372 (H2O), [α]D 20 153.9-5.0°.
~0 Citings
48. An interesting oil-bearing monocotyledonous plant

By Pieraerts, J.
From Matieres Grasses (1924), 16, 6674-81. Language: Unavailable, Database: CAPLUS
SciFinder® Page 36
Sedge (Cyperus esculentus L.) tubercles contain about 20-7% of oil, 15-20% of sucrose and 25-30% of amylaceous
matter. A sample of cold-pressed oil prepd. in the lab. had d15 15 0.9176; solidifying point, clear at +1°; [α]D 22 +0.06;
spectroscopic examn. showed no absorption; Crismer no. (1 vol. of oil, 2 vols. of 99.6% alc. in sealed tube) 85°; n25
1.4650; Maumené no. 27°; acid no. 1.70 (= 0.85% oleic acid); sapon. no. 191.3; sapon. no. of acetylated oil 195.2; Ac
no. (via André) 4.55; Reichert-Meissl no. 0.2; I no. 76.89; insol. fatty acids + unsapon. 94.90%; unsapon. 0.62%; glycerol
8.82%; elaidin test gave solid mass in less than 1 hr.; hexabromide test, negative; Baudouin, Halphen and Milliau-Becchi
reactions all negative; alkaloidal compds. none; cyanogenetic compds. none; flash point (Luchaire) 247°; flash point
(open cup) 283°; burning point 362°; fluidity (Barbey) 119° at 35°, 204° at 50° (pure colza oil 100° at 35°); not the least
sign of drying properties after exposure in a thin film for 3 months. The insol. fatty acids gave: m. p. 38.6°; solidifying
point, superfused at 21° and partly solidified after several hrs.; neutralization no (direct) 199.5, equiv. to mean mol. wt. of
280.7; neutralization no. (indirect) 208.9, equiv. to mean mol. wt. of 268.5; I no. 75.1; sapon. no. of acetylated acids
213.0. The so-called "Pb-ether" method gave 80% of liquid acids and 20% of solid acids. The liquid acids gave:
neutralization no. (direct) 180.1, equiv. to mean mol. wt. of 311.4; neutralization no. (indirect) 212.1, equiv. to mean mol.
wt. of 264.4; I no. 84.6; n22 1.4563; [α]D 20 +0.11; hexabromide test negative. They consist mainly of oleic acid (identified
by transforming into elaidic acid, white crystals from 95%. alc., m. 44.2°, I no. 89.8; and by transformation into
dihydroxystearic acid via Hazura, tabular crystals from 95% alc., m. 132.5°, neutralization no. 178, equiv. to mol. wt. of
178, neutralization no. after acetylation 418.4), together with a small amt. of linoleic acid (identified as satiric acid in the
residue after elimination of the dihydroxystearic acid, pyramidal crystals, m. 173.5°) and of an unidentified (probably a
hydroxy) acid. The solid acids m. 52.5°, neutralization no. (direct) 226.5, equiv. to mean mol. wt. of 247.6; neutralization
no. (indirect) 230.6, equiv. to mean mol. wt. of 243.2; I no. 9.80 (corresponding to 9.80% oleic acid). They consisted
mainly of myristic acid with a small amt. of palmitic acid (technic of identification by purification and fractional crystn.
described in detail). The qualities and possible uses of the oil are described.
~0 Citings
49. Essential oil of Daucus carota L. I.

By Asahina, Y.; Tsukamoto, T.
From Yakugaku Zasshi (1925), No. 525, 961-9. Language: Unavailable, Database: CAPLUS
An attempt was made to det. the nature of the unesterifiable O of daucol (cf. Richter, C. A. 4, 299). Three essential oils
prepd. in 1921 from fruit, fruit mixed with stems, and stems alone gave, resp.: d22 0.9088, 0.9270, 0.9584; [α]D 20 -5.98°,
+1.04°, +5.06°; acid no. 0, 2.86, 24.91; sapon. no. 74.08, 69.69, 65.97. Fresh oil from fruit and stems had d22 0.9220,
[α]D20 0, acid no. 1.17 and sapon. no. after acetylation 156.8. The analysis of the different fractions for % C and H
shows, resp.: (1) b7 110-9°, 79.93, 10.35; (2) b7 119-24°, 76.91, 9.34; (3) b7 124-30°, 80.13, 10.61; (4) b7 130-40°, 83.26,
11.83; (5) b7 139-42°, 82.20, 11.82; and (6) b7 142-8°, 81.40, 11.68. The fractions (4), (5) and (6), which should contain
daucol (I), contain a sesquiterpene C13H26O (II) and no I could be identified in these or in any of the other fractions. On
oxidizing the higher fractions with KMnO4, a cryst. compd., C13H29O3 (III), m. 142°, was obtained, showing that II
absorbed 2OH, and changed to a glycerol. II can be sepd. as the Hg salt and subsequently freed as the original alc. by
treating with H2S. It b15 109°, has d4 15 0.9646, nD 5 1.4912, mol. refraction 66.79 (calcd. for 1 double bond, 68.13). II is
named carotol. It takes up no II by catalytic reduction; on oxidation with KMnO4, it gives III, a glycerol; and it forms a di-
Br deriv., showing, therefore, that II is a dicyclic sesquiterpene having a double bond. II dibromide heated with BzOAg
and boiled with alc. KOH gives I. When III is treated with anhyd. BzOH, I also is formed. I is, therefore, the anhydride of
III.
~0 Citings
50. Cellulose acetates for artificial silk, etc.

By Zdanowich, J. O.
From No Corporate Source data available (1925), GB 227134 19250105, Language: Unavailable, Database: CAPLUS
Directly spinnable cellulose acetate acetylation solns. or mixts. are rendered stable as to viscosity by adding H2O or
other stabilizer such as aq. MeOH, EtOH, AmOH, lactic or formic acid, chloral hydrate, H2O2 or glycerol. Solns. thus
prepd. remain in spinnable condition for several weeks.
~0 Citings
51. The constitution of starch

By Peiser, Elizabeth.
From Hoppe-Seyler's Zeitschrift fuer Physiologische Chemie (1926), 161, 210-7. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 37
Starch is an individual substance, except for about 1% of impurity contained in the outer wall of the grains, and is not a
mixt. of amylose and the hypothetical amylopectin. The supposed violet I reaction of amylopectin as contrasted to the
blue reaction of amylose is merely an illusion. starch is stained uniformly blue by I, the violet color obtained With an
excess of reagent being merely dissolved I which can be removed by CHCl3, leaving a pure blue. In fact the blue also
can be removed completely by extn. with sufficient CHCl3. The outer coating of the starch grain consists of Ca3(PO4)2,
SiO2 and a nitrogenous substance, probably a protein. When the grains are freed from this coating they no longer swell
and form a paste but behave like insulin. Treatment of dried starch paste with Ac2O in the cold gives an acetyl starch (I),
[α] 276.3°, C43H56O42Ac26. The same product is formed no matter at what stage the acetylation is interrupted. It
contains 8 monosaccharide and 26 Ac groups, the terminal monosaccharides carrying 4 Ac groups each and the
intermediate ones 3 Ac groups each. Hydrolysis of I by alc. NaOH gives a product with all the properties of amylose.
When the acetylation of starch is performed at 55°, the product is an acetyltetrasoc-charide (II), [α] 240°, C21H23OnC14 of
the same mol. arrangement as I. The tetra-saccharide obtained from this by removal of Ac gives a blue I reaction even in
very dil. soln. A 2nd acetyltetrasaccharide with I less Ac group is obtained by treatment of I in CHCl3 with PCl5. It takes
up another Ac group when treated With Ac3O, yielding II. Starch is probably a simpler substance than commonly
supposed, the most stable linkages present being those binding the pairs of hexose into disaccharides. All of the
linkages are of a chem. nature, however, since only chem. methods dissolve them. Sol. starch prepd. by heating starch
in glycerol at 190° is less readily acetylated, probably because of anhydride linkages present.
~0 Citings
52. Commercial notices and scientific data on ethereal oils

No Author and Editor data available
From Ber. von Schimmel & Co. (1926), 3-133. Language: Unavailable, Database: CAPLUS
SciFinder® Page 38
Among comprehensive reviews of the literature and com. notices appear the following data covering research of the labs.
of Schimmel & Co. Valerian oil obtained from dried Thuringian valerian roots in 0.49% yield, was yellow-green, had d15
0.9623, nD 20 1.48599, acid no. 5.6, ester no. 128.8, was miscible with 90% EtOH in all proportions but was not wholly
dissolved by 10 vols. of 80% EtOH. Light camphor oil is recommended as a substitute for oil of turpentine, e. g., Type
CLA, which is very mild, has d. 0.86, b. 167-195°, flash point 41°; Type CLS, with stimulating odor, d. 0.88, b. 176-210°,
flash point 44°; Type FL, with odor of conifers, d. 0.89, b. 180-210°, flash point 46°. Citronella oil. Two samples of
Ceylon oil were of inferior quality, because of their low geraniol content (26.4 and 28.2%, resp.). One was probably a by-
product of the production of geraniol, and the other by its dextro-rotation showed adulteration, probably by a fraction of
camphor oil. A sample from Holland, which was of high quality based on its ester no., had much too high d. (0.9559) and
contained considerable BzOH, probably as BzOCH2Ph. Coriander oil. Besides adulteration with anise oil and anethole,
already reported, a sample was found with terpineol. It had too high d., too low rotation and too high acetylation no.
Elemi oil. A sample of elemi resin from Bandjarnegara (Java), which was distinguished from ordinary grades by its dirty-
gray color changing to brownish and by its low oil content (16.7%), gave a colorless oil, d15 0.8517, [α]D 104°35' (after 4
mos. 68°10'), nD 20 1.47779, and dissolved in 4.5 vols. of 90% EtOH with strong phellandrene reaction. Bergamot oil.
The consts. of 4 oils adulterated in different ways are compiled with those of pure oil. The addn. of lemon oil terpenes to
2 of the oils was concluded, while the 3rd oil had been adulterated with an ester of lauric acid and a little glycerol acetate
to compensate for its low ester no. resulting from the other adulterant. The 4th oil had a high terpinol acetate content.
Lemon oil. In one case adulteration with oil of turpentine was detected, and in another case with terpenes and a phthalic
ester. Still another sample contained a large proportion of terpineol. Eucalyptus oil. Oils from the Eucalyptus dives from
Australia had a higher d. and in some cases lower rotatory power than reported by Gildemeister and Hoffmann. Oils
from reliable sources had d15 0.8969-0.9188, [α]D -46°55' to -61°48', nD 20 1.48209-1.48577 and dissolved in 0.5-1.3
vols. of 80% EtOH and were miscible in all proportions with 90% EtOH, contained 43-50% piperitone and a high
phellandrene content. An oil of Eucalyptus macarthuri Deane et Maiden had d15 0.9307, [α]D 4°40', nD 20 1.47534, acid
no. 2.6, ester no. 166.1, ester no. after acetylation 212.8 (69.6% total geraniol) and dissolved in 3 vols. of 70% EtOH.
Galangal oil. Oils prepd. during the yr. had properties which in some respects did not fall within the limits already known
heretofore. They had a spicy odor suggesting cardamom oil or myrtle oil, with d15 0.915-0.924, [α]D -1°30' to -5°30', nD 20
1.476-1.482, acid no. up to 3.6, ester no. 13-17, ester no. after acetylation 40-67, soly. 0.2-0.5 part of 90% EtOH. In 2
oils there were 3% eugenol, of which 25% was found by Hoist in an oil. Over 3% eugenol indicates adulteration.
Geranium oil. An oil from Stellenbosch (Cape Colony), probably from Pelargonium graveolens Ait., was bright yellow,
had d15 0.8952, [α]D -15°55', nD 20 1.4781, acid no. 5.6, ester no. 20.5, ester no. after acetylation 207.2, ester no. after
formylation 56.0. In odor it was inferior, even after rectification, to oils from other sources. Inchi grass oil, from
Cymbopogon caesius Stapf, had d15 0.9250, [α]D -34°25', nD 20 1.48895, acid no. 0.9, ester no. 11.2, ester no. after
acetylation 98.9, was not completely sol. in 10 vols. of 80% EtOH but was sol. in 0.3 vol. of 90% EtOH (slight
opalescence). Its odor did not resemble palmarosa oil, as described by others, but rather Ceylon lemon oil. Lavender oil
was repeatedly found to contain glyceryl acetate and phthalic ester. The detection of adulteration has recently become
more difficult, on account of the addn. of several artificial esters in small quantities. Two oils were apparently adulterated
with geraniol and perhaps also with geranyl acetate, though nothing could be ascertained from the consts. An alleged
marjoram oil showed complete variation in odor and consts. from those of the true oil. Samples of the rind of Cryptocaria
pretiosa Mart. (Mespilodaphne pretiosa Nees et Mart., and Ocotea pretiosa Benthe et Hook) from Brazil gave on distn.
1.31% of a brown oil with odor resembling cinnamon, d15 1.1263, [α]D -0.8', nD 20 1.52787, sol. in 7.2 vols. of 80% EtOH.
Oil of Nardostachys jatamansi, obtained in 3.43% yield from roots from Japan, was olive-green with an odor resembling
valerian oil, d15 0.9819, [α]D -15°15', nD 20 1.51790, acid no. 5.6, ester no. 18.7, not completely sol. in 10 vols. of 80%
EtOH, but miscible in all proportions with 90% EtOH. Nigella oil, from the seeds of Nigella damascena L. in 0.37% yield,
was yellow with strong blue fluorescence, had d15 0.8985, [α]D -4°49', nD 20 1.49970, acid no. 1.1, ester no. 14.0, ester
no. after acetylation 17.7, dissolves in about 15 vols. of 90% EtOH and about 4 vols. of 95% EtOH. Peppermint oil. An
oil from Chile from cultivated plants had d15 0.9026, [α]D -29°42', nD 20 1.46638, acid no. 0, ester no. 41.1, ester no. after
acetylation 189.5, dissolves to a turbid soln. in about 4 vols. of 70% EtOH and gives a clear soln. with 1.5 vols. of 80%
EtOH which becomes opalescent when dild., and has an unpleasant odor, perhaps because of imperfect distn. Two
samples of oil from China were similar in odor and consts. to Japanese peppermint oil. Adulteration of peppermint oil
was often found, sometimes in a very crude way. A sample of "dementholized" oil bore no relation to peppermint oil, but
probably came from a eucalyptus oil. Rose oil was in 1 case adulterated with what was probably a lauric acid ester and
in another oil a myristic acid ester was identified as an adulterant. Rose extract oils, as shown by analysis of numerous
samples from different sources, differ from the usual oils obtained by steam distn. by their high d., n, dextro-rotation, acid
no, and ester no. The dextro-rotation does not depend upon non-volatile extractive substances, as shown by distn.
Rose ext. oil from fancy roses contained only about 0.5 as much geraniol as that in other grades. Adulteration of
rosemary oil could be recognized by the odor, and particularly by acetylation. Sandalwood oil from western Australia,
which sometimes is offered as East Indian oil, differed from the latter in odor and in its optical rotation. PhCH2OH and
terpineol were found as adulterants. Oil of spike. An alleged oriental product from London had other properties, and
judged by its odor was a white blended camphor oil. Oil of turpentine. So-called Strasbourg turpentine from white fir and
silver fir from Bolzano had d15 1.0033, [α]D -7°22', nD 20 1.52359, acid no. 83.1, ester no. 8.4. The oil obtained from it by
steam-distn. (in 27.2% yield) had d15 0.8650, [α]D -7°15', nD 20 1.47211, acid no. 0, ester no. 11.2: dissolves in 6.2 vols.
of 90% EtOH. Distn. (at 749 mm. pressure) of oil from Ladenburg spike gave 56% at 160-4°, 20% at 164-70°, 9% at
170-80° and 15% above 180°. A silver fir turpentine from Upper Alsace had similar properties. A sample of cinnamon oil
was found to be only cinnamic aldehyde.
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53. Acetylation of aniline and the toluidines in anhydrous glycerol
By Gasopoulos, I.
From Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen (1926), 59B, 2187. Language:
From 1 part PhNH2, 2 parts AcOH and 0.5 part anhyd. glycerol refluxed 2.5 hrs. is obtained 86.8% almost pure AcNHPh,
m. 114°. o-AcNHC6H4Me, m. 110° after recrystn., is obtained in 46% yield; m-compd., m. 64°, 79.1%; p-compd., m.
153°, 90%.
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54. Acetic acid

By Suida, H.
In processes such as described in Brit. 230,447 (C. A. 19, 3272) there are employed as solvents acylated or acetylated
products formed from compds. such as glycol, glycerol, BuOH, heavy wood tar oils, or brown coal creosoles or other
alcs. and phenols. Am butyrate, hexyl acetate and AmOAc also may be used. Acetylation of the solvent may be effected
in the same app. used for the extn. and production of concd. HOAc.
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55. Stereochemistry of the tetrahedral carbon atom. VI. Configuration of the glycols formed by reduction of
aldehydes with the zinc-copper couple
By Kuhn, Richard; Rebel, Otto
cf. C. A. 21, 2871; Ott and Schroter, C. A. 21, 2090. The observation that hydrolysis of cis-ethylene-oxide-dicarboxylic
acid yields racemic acid (1) exclusively while the trans-acid under the same conditions gives a mixt. of I and the meso-
acid (II) cannot be explained on a geometrical basis alone and presumably depends in some as yet not clearly
recognizable way on the energy content of the isomers. In a search for similar phenomena in simpler cases where for
the configuration of the resulting glycols that of the starting materials would not have to be considered at all, K. and R.
studied the reduction of aldehydes with the Zn-Cu couple. On purely geometrical grounds, in such reactions there could
be formed 25% each of the d- and l- and 50% of the meso-glycol, but in spite of many efforts to detect isomers in every
case only the dl- or the meso-form alone was found. The configuration of the reduction products of OHCCO2H and BzH
was established directly by the resolvability into optical antipodes of the resulting I and [PhCH(OH)]2, resp., that of the
diols formed from CH2: CHCHO, MeCH: CHCHO and PhCH: CHCHO by degradation to I or II, the rupture of the double
bonds being effected with O3. In the latter reaction the choice of solvent is of the greatest importance; in EtCl, CHCl3 and
CCl4 there are formed gelatinous, highly polymerized ozonides which are decompd. only with great difficulty and on
subsequent oxidation with Br water give only traces of [CH(OH)CO2H]2. In AcOH, however, the ozonides are not pptd.
and the satn. of the double bonds, which can be followed by titration with Br, proceeds much more rapidly, the O3 is
completely utilized, the resulting glycol diozonides are smoothly decompd. by boiling in the AcOH and subsequent
treatment with Br gives the desired [CH(OH)CO2H]2. The HO groups must also be protected by acetylation; thus [Ph-
CH:CHCH(OH)]2 with O3 in AcOH gives only traces of II, while its diacetate under the same conditions gives 46%. d-
[CH(OH)CO2H]2 in AcOH undergoes no change in rotation on long treatment with O3 and rearrangements of the
[CH(OH)CHO]2 are also excluded, for under the same conditions are obtained exclusively the meso-or the dl-form.
There remains the possibility that mol. groupings richer in energy, formed transiently during the reactions, undergo
rearrangements in the -CH(OH)-CH(OH)- residues although, formally, these remain untouched in the decompn. of the
ozonides. K. and R. found that aldehydes RCHO give dl-[RCH(OH)]2 when R = CO2H and CH:CHMe, and the meso-
glycols when R = Ph, CH: CH2 and CH:-CHPh, there being no recognizable relation between the nature of R and the
configuration of the resulting glycol. Divinyl glycol, b4 92°, b12 98° d4 20 1.006, nD 20 1.4700, is obtained in 53 g. yield
from 200 g. CH2: CHCHO, which, in turn, is obtained in 150 g. yield from 1 kg glycerol and MgSO4 at 330-40°. With Pt
sponge and H, in AcOH it quant. gives meso-3,4-dihydroxyhexane (α,β-diethylethylene glycol), m. 88° b10 91°. α,β-
Dipropenyl glycol (yield, 12-5%), b2 122°. Diacetylhydrocinnamoin m. 124-5° (Thiele, Ber. 32, 1296(1899), gives 118-9°).
1,6-Diphenyl-meso-3,4-dihydroxyhexane (α,β-bis[β'-phenylethyl]ethylene glycol), m. 132°; diacetate, m. 70°.
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56. Polyvinyl alcohol
By Herrmann, W. O.; Haehnel, Wolfram
This summary of H. and H's unfinished investigation is published now because of the appearance of Staudinger's
address (C. A. 21, 1271). Polymeric forms of vinyl alc. have been obtained from its polymeric esters. A striking property
of this polyvinyl alc. (I) is its carbohydrate-like nature which apparently places it between sugar and starch. It has also
been prepd. on a com. scale from C2H2. Sapon. of the polymeric esters with either acids or alkalies gives the I in solid
form, the method of procedure depending on the nature of the raw material; thus, with a brittle, pulverizable polymeric
vinyl acetate, 80 g. of the finely powd. ester is stirred 1 h. with 60 g. KOH and 45 g. NaOH in 500 g. cold or hot alc.,
whereas with the elastic forms of the ester an alc. soln. is stirred into alc. KOH or vice-versa. The I may sep. in the most
varied forms (crusts, flocks, fibers, sometimes powders). Acid sapon. is effected by passing HCl into a boiling alc. soln.
of the ester or by boiling the alc. soln. for some hrs. with a little H2SO4. The product contains considerably less ash than
that obtained by alk. sapon. The alkali product is uniformly light yellow to light brown, while the color and d. of the acid
products vary widely, depending on the nature of the raw material. I has a great power to adsorb inorg. salts but can be
purified to some extent by repptn. from H2O with alc. Most forms are sol. in H2O but there are also insol. black
modifications. I is tasteless and odorless. Its mol. wt. cannot be detd. by the Rast method because it decomps. at the m.
p. of camphor; by the osmotic method was obtained an approx. value of 868. Under 1000 atm. I m. 250° to a very thick,
hard, elastic material, d. 1.5810, which can readily be worked; pptd. I has an apparent d. ranging from 0.054 to 0.360.
The heat of combustion of I is 5902 cal. per g. The sol. forms dissolve in H2O in all proportions with no appreciable heat
tone, the 5, 10 and 20% solns. showing d20 1.0079, 1.0226 and 1.1435, resp.; the 30% soln. gelatinizes. The Engler
degree E of the 5, 10 and 20% solns. at 20° is 1.35, 2.54 and 58.8, resp.; the sp. viscosity z is 2.9, 9.2 and 274.4. I is
insol. in most org. solvents; the clear colloidal solns. in glycerol and glycol gelatinize on cooling; that in hot PhOH
remains thin on cooling if the PhOH contains a trace of H2O; evapn. of the solns. on smooth surfaces leaves exceedingly
viscous films. I behaves as a reversible colloid like Hb, globulin, albumin and dextrin, can be purified by dialysis,
functions almost exclusively as a hydrosol; unlike gelatin it swells but little in H2O. It is well adapted to use as a
protective colloid for metals, hydroxides, oxides, sulfides, etc. Under 30 atm. it undergoes no alteration up to 150°; at
200-20° it changes into an exceedingly hard, horny, light to dark brown mass of the same compn. as the original I but
less sol. in glycerol, glycol and H2O and more sol. in hot linseed and castor oils; acetylation of the pressed product gives
the typical polymeric vinyl acetate. I adds Br to form compds. whose structure has not yet been cleared up; thus 18 g. I
and 105 g. Br allowed to stand 4 days in 9 l. H2O yield a yellow ppt. contg. 54.2% Br, converted by boiling H2O into the
black, H2O-insol. form of I. A neutral 10% aq. soln. of I with Cl at room temp. gives a brown H2O-insol. substance, also
changed into the black I by boiling alkalies. With H2O2 I gives a substance somewhat richer in O and poorer in C but with
the same properties as I. I is apparently not oxidized by KMnO4 or CrO3; I, K3CO3 and H2O give CHI3; evapn. in vacuo
with aq. NaOH yields a dark brown homogeneous substance, apparently a Na polyvinyl alcoholate trihydrate; I forms an
acetal with BzH; it shows no lignin reactions but gives pos. Carletti (thymol and menthol) and Fleig and Ihl (indole and
peppermint oil) carbohydrate reactions; it is converted back into polymeric vinyl esters by acids or their anhydrides and
into the xanthate by NaOH and CS2. With HCHO it forms compds. allied to the amyloform of starch; these are odorless
substances, somewhat more elastic than amyloform, insol. in H2O, do not swell, more stable towards heat than
amyloform, are fusible, slowly lose HCHO with dil. acids and alkalies, form esters. Like crude rubber, I can be vulcanized
with S, with or without accelerators; cold vulcanization gives soft gumlike, very elastic products, hot vulcanization a hard
black mass which can be readily worked. I fed to mice, either directly in the form of a colloidal soln. purified by dialysis or
in milk, produced no discernible harmful effects.
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57. Gonyo (Antrocaryon nannani, de Wild)

By Pieraerts, J.; Ipatieff, N.
From Matieres Grasses (1927), 19, 7943-4,7974-6,7999-8000,8028-9. Language: Unavailable, Database: CAPLUS
SciFinder® Page 41
The kernel has the following compn. on the dry basis (H2O 3.98%); ash 4.77, total N 3.48, crude protein (N × 6.25) 21.75,
oil 71.65, cellulose (via Weende) 1.15, pentosans trace, furfuroids none, reducing sugars none, sugars hydrolyzable by
invertase (as sucrose) 0.43, total P2O5 2.03, lecithin P2O5 0.47%, alkaloids none, tannin none, cyanogenetic glucosides
none, resins none, toxalbumin none, bitter principles none. The oil cake remaining after extn. with petroleum ether and
drying had the following compn.; ash 16.83, total N 12.27, crude protein (N × 6.25) 76.68, albuminoid N (by Grandeau's
1% AcOH method) 11.41, true albuminoids 71.31, fiber 4.05, sugars hydrolyzable by invertase (as sucrose) 1.55, P2O5
7.16%. The oil extd. by petroleum ether had the following consts.: d14 14 0.9137, n18 1.4717, Crismer no. (1 cc. oil, 2 cc.
99.4% EtOH in sealed tube) 73°, Maumené no. 53°, sp. reaction temp. (according to Thomson and Ballantyne) 120°,
neutralization no. 0.8 (= 0.4% oleic acid), sapon. no. 200.6, ester no. 199.8, I no. 84.7, Ac no. (via E. André) 2.83,
sapon. no. of the acetylated oil 205, Hehner no. 95.31%, glycerol 10.74% (calcd. from the ester no. 10.92%), lecithin
P2O5 0.65%, unsapon. 1.61%, Reichert-Meissl no. 0.3, Polenske no. 0, Halphen's reaction (CS2) negative, Beaudouin's
reaction negative, Milliau-Becchi reaction mirror and grayish black deposit of metallic Ag, elaidin test very hard canary-
yellow (with brownish tinge) mass in 30 min., the underlying acid being perfectly colorless, hexabromide test negative.
Consts. of the mixed fatty acids: m. 43.5-45.5°, solidifying pt. 40-37.5°, n50 1.4517, neutralization no. 192 (= mean mol.
wt. 292.1), sapon. no. 203 (= mean mol. wt. 276.3), I no. 85.4, Halphen's test (CS2) negative, Beaudouin's test negative,
Milliau-Becchi reaction fine Ag mirror, elaidin test hard mass in 15 min., hexabromide test negative. Consts. of the liquid
acids: about 70% of the total acids, abs. I no. 121.8 (showing that the acids consist of 65.2% oleic and 34.8% linoleic
acids), neutralization no. 197.5 (= mean mol. wt. 284), hexabromide test negative. Consts. of the solid acids: about 30%
of the total acids, m. 59-60°, solidifying pt. 56-55°, neutralization no. 203.4 (= mean mol. wt. 277.2), sapon. no. 212.9 (=
mean mol. wt. 264.6), I no. 4.3 (which, from the abs. I no., shows the presence of 3.5% of liquid acids). Presence of oleic
acid was proved by its transformation into elaidic acid by acid mercuric nitrate, and by its conversion into dihydroxystearic
acid by KMnO4 oxidation. Presence of linoleic acid was proved from the consts. of its tetrabromide and from the consts.
of the sativic acid isolated from the KMnO4 oxidation products of the liquid acids. The solid acids are shown to consist of
stearic acid 35, palmitic acid 45, myristic acid 20% (analytical data of the investigation are given). The presence of
lecithin was proved by identifying the P2O5 and choline resulting from its hydrolysis (analytical data are given). The
consts. of the oil are quite similar to those of Brazil-nut oil. The possible economic importance of Gonyo is briefly
discussed.
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58. Glycerolphosphoric acids. IV

By Karrer, P.; Benz, P.
From Help. Chim. Acta (1927), 10, 87-91. Language: Unavailable, Database: CAPLUS
Further evidence is given of the specificity of pptn. of the double Ba salt with Ba(NO3)2 (cf. C. A. 20, 1218) as a test
distinguishing glycerol-β-phosphoric acid (1) from the α-isomer (II). The Ba salt (III) of d-II was acetylated to give Ba
diacetyl-d-glycerolphosphate (IV), crystals from hot alc., [α]D 18 = 2.0°. IV, hydrolyzed to III by Ba(OH)2, gave no test for
I, and on reacetylation gave a IV having [α]D 18 1.81°. This completes the evidence that derivs. of II do not rearrange to
give I on mild treatment with alkali, and that lecithin is a deriv. of I in much larger proportion than of II.
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59. Acetylation of aniline in water-free glycerol

By Sakellarios, Euklid
Contrary to the statements of Gasopoulos (C. A. 21, 394), glycerol does not favor but rather impedes the acetylation of
PhNH2; from 20 g. PhNH2 and 40 g. AcOH without glycerol S. obtained 86% AcNHPh after heating 2.5 hrs. on a sand
bath. With the addn. of 10 cc. of xylene, however, the same result can be obtained with only 20 g. AcOH. From equimol.
amts. of PhNH2 and acetin heated 2.5 hrs. at 105-200° was obtained only about 30% PhNHAc. o-MeC6H4NH2 with 2
parts AcOH gave 57.5% MeC6H4NHAc; G. with glycerol obtained only 46%.
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60. Sulfur-containing derivatives of glycerol

By Fromm, Emil; Kapeller, Regine; Taubmann, I.
SciFinder® Page 42
The compds. (I and II) obtained by the action of NaHSO3 and Na2SO3, resp., on epicholorohydrin (III) have hitherto been
assigned the structures ClCH2CH(OH)CH2SO3H and HOCH(CH2SO3H)2, structures apparently confirmed by Pazscke's
observation that II is formed by boiling I with Na2SO3. But when I is boiled with NaOH it decomps. with loss of Na2SO3,
identified by its reduction to SnS2 with SnCl2 and HCl by the Böttger method. S so easily split off cannot be present as a
sulfonic acid but must be in a sulfite ester, i. e., I must be ClCH2CH(OH)CH2OSO2H, decompd. by alkalies into Na2SO3
and III which then give II. To det. whether or not II also contains S easily split off is not easy for the Na salt of II is, from
its method of prepn., contaminated with Na2SO3, an impurity not removed when the Na salt is converted into the difficulty
sol. Ba salt, since BaSO3 is also difficulty sol., and all prepns. of the Na or Ba salt give the Böttger SnS2 reaction. But if
the salt of II is repeatedly evapd. with HCl, which would decomp. all the metal sulfite and any sulfite ester present, the Ba
salt of the unchanged II can still be pptd. with BaCl2, showing the III with a primary sulfite gives a sulfite ester and with a
secondary sulfite a true di-SO3H acid. PhCH2SNa and III give S,S'-dibenzyl-α,α'-dithioglycerol (IV); this with HCl, Ac2O
and BzCl gives oily products which cannot be distd. but that Ac2O gives the mono-Ac deriv., AcOCH(CH2SCH2Ph)2 (V),
was shown by oxidizing the oily V to the cryst. disulfone, AcOCH(CH2SO2CH2Ph)2 (VI). IV itself with acid KMnO4 gives
the corresponding β,β'-dibenzylsulfoneisopropyl alc. (VII). crystals with 1 H2O, which can be converted into V by
acetylation. K2Cr2O7 and concd. acids merely remove the H2O of crystn. but the ketone CO(CH2SO2CH2Ph)3 (VIII) was
finally obtained from CO(CH2Cl)2 and NaSCH2Ph and subsequent oxidation of the oily product with KMnO4. The H
atoms of the CH2 groups between the SO2 and C:O groups in VIII are labile, as would be expected, and readily
replaceable by metals and alkyl groups. VIII dissolves more readily in alc. alkalies than in alc. itself. Methylation could
not be effected in alc., evidently because the sulfone is decompd. by boiling alkalies, forming PhCH2SO2H, easily
identified as (PhCH2)2SO2 when the alkali cleavage is effected in the presence of PhCH2Cl. VIII does not react with the
usual ketone reagents (PhNHNH2, NH2OH, N2H4.H2O), but does form mercaptoles. Thus with PhCH2SH and HCl is
obtained an oily dibenzyl mercaptole, oxidized to the cryst. sulfonal (IX), (PhCH2SO2)2C(CH2SO2CH2Ph)2, also obtained
from 2 mols. PhCH2SH, CO(CH2Cl)2 and dry HCl, subsequent treatment of the oily mercaptole with 2 mols. PhCH2SNa
and oxidation of the resulting tetrasulfide. IV m. 59°. VI m. 159-60°. VII m. 215° and, anhyd., 206-8°, loses its H2O in
boiling glacial AcOH or H2SO4 (3 parts concd. acid to 1 of H2O) but not when heated alone 2 hrs. at 130° or refluxed in
alc. NaOH. VIII m. 182°. IX m. 198°.
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61. Preparing cellulose for acetylation, etc.

By Klein, F. G. C.
Cellulose (such as cotton which is to be acetylated), polysaccharides, protein materials and other colloids are maintained
in swollen condition in which they are readily reactive, by replacing the adsorbed water, at least partially, by a substance
(such as diacetin in treating cotton preliminary to acetylation) capable of swelling and miscible with or sol. in the
acetylating or other reagents to be used or the solvents used with such reagents. In the production of cellulose and
ethers, such as benzyl cellulose, in which the reaction is effected in alk. soln., glycerol or glycol may be used for the
pretreatment. The pretreatment is also applicable in the prepn. of viscose, cuprammonium cellulose solns. and solns. of
cellulose in strong acids.
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62. Polymerization and condensation. IV. Experiments on glycidol acetate

By Levene, P. A.; Walti, A.
From Journal of Biological Chemistry (1928), 79, 363-76. Language: Unavailable, Database: CAPLUS
cf. C. A. 22, 59. Glycidol acetate was allowed to stand for 5 days at 135-40° and for several weeks at 12-3° and the
polymerization product fractionated. Among the products obtained were: the dimeric form of glycidol acetate, mol. wt.,
226, which on standing was further polymerized; incompletely acetylated glycerol; monoacetin; triacetin; and polymers of
glycidol acetate. Conclusion.-Glycidol acetate has a greater tendency to polymerize than propylene oxide, glycidol or
CO(CH2OH)2, but a lesser tendency to form condensation products than these substances. MeCOCH2OAc showed no
tendency to polymerize or form condensation products.
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63. Konjak mannan

By Ohtsuki, Torao
From Acta Phytochimica (1928), 4(No. 1), 1-39. Language: Unavailable, Database: CAPLUS
SciFinder® Page 43
A crude powder prepd. from the tubers of Amorphophallus konjak yielded when taken up in water and ppt. with alc. a
mannan having [α]D 14 = -42.8, which caused no lowering of f. p., and yielded on hydrolysis mannose and glucose in the
proportion 2:1. When treated with a malt diastase, or yeast, the mannan gave a substance (Konjak mannan) with the
same rotation, and yielding the same products of hydrolysis but with a viscosity 7.7 times less than the mannan. By
treating with the diastase for long periods of time a trisaccharide was obtained (levidulinose) having a rotation [α]D 4 = -
15.6, and yielding mannose and glucose on hydrolysis. Heating at 235° with glycerol gave a dissocn. product that is
much more sol. in water, of lower viscosity and the same rotation as the original material. The particles are of the same
size as a trihexosan. The substance reassociated on standing to a higher colloid, and gave on hydrolysis mannose and
glucose in the proportion 2:1. The acetylated product had a mol. wt. (detd. by cryoscopic method) corresponding to a
hexoseanhydride acetate.
~1 Citing
64. Condensation of glycerol

By Rangier, M.
From Compt. rend. (1928), 187, 345-6. Language: Unavailable, Database: CAPLUS
cf. C. A. 7, 3113; 16, 2038, 3224. In view of the contradictory information in the literature, R. has studied the
condensation of glycerol by heating with 2% AcONa at different temps. and times. The reaction products were
acetylated, and the following acetins were isolated and analyzed: (AcO)4(C3H5)2O, b2 164-5°; (AcO)5(C3H5)3O2, b2 194-
5°; (AcO)6(C3H5)4O3, b2 224-5°; (AcO)7(C3H5)5O4, b2 254-5°; (AcO)8(C3H5)6O5, b2 284-5°, all of which are viscous
liquids, and which were obtained in yields of 10-82 g. from 100 g. glycerol. In pushing the condensation very far, a cryst.
acetin was obtained which appears to be the same as a diacetin of the homologous diglyceric alc. from dichlorohydrin,
reported by Fauconnier and Sanson (see Bull. soc. chim. 48, 236(1887)).
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65. Resins, waxes, balms, etc.

From No Corporate Source data available (1929), FR 662603 19290809, Language: Unavailable, Database: CAPLUS
Products of the nature of resins, waxes, balms, suppling agents, etc., are made by the reaction of monobasic org. acids
of high mol. wt. or polybasic acids or their derivs. or natural or artificial resin acids or their salts with alkylene monoxides
or their derivs., the latter not contg. more than one free hydroxyl group, such as the corresponding halohydrins in the
presence or not of condensing agents or acid fixing agents, and acylating the products obtained if necessary. In
examples, (1) colophony is heated under pressure to 160-170° with (C2H4)2O and the product is acetylated giving a balm
like resin; (2) a resin ester obtained from colophony and glycerol is heated to 140° with (C2H4)2O giving a product with
lower acid index. Other examples are given.
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66. Oleiferous Allanblackia. Preparation of pure stearic acid

By Pieraerts, J.; Adriaens, L.
From Matieres Grasses (1929), 21, 8510-4,8539-41. Language: Unavailable, Database: CAPLUS
Seeds of Allanblackia flboriunda var. Kisonghi contained 3.56% H2O on the dry basis, total ash 1.79 (H2O insol. ash
0.68, H2O sol. ash 1.11), total N 0.58, nitrogenous matter (N × 6.25) 3.63, fatty matter 60.16, pentosans 0.31, cellulose
4.39, ash alky. as K2CO3, on total ash 40.02, on H2O sol. ash 64.54%. After complete extn. with petroleum ether the oil
cake contains 1.5% total N, 9.38% nitrogenous matter, 2.78% reducing sugars, 0.85% pentosans, 11.65% cellulose,
0.55% P2O5, carbohydrates other than sugars (hydrolyzed in 3% H2SO4) 8.13%; d100 100 of fats 0.8917 or at 15° (Allen
factor) 0.9461, m. p. 38.5-40°, solidification point 37-36°, acid no. 22.9, acid as oleic acid 11.45%, sapon, no. 197.9,
ester no. 174, I no. 42.33, Crismer no. 71.5, nD 66 1.4471, unsaponifiable 1.60%, Hehner no. 95.84%, sapon. no. of
acetylated oil 212.8, acetyl no. 19.98, Beaudoin test negative, Halphen test negative, Milliau-Becchi test positive, calcd.
glycerol 18.81%, obtained 10.12%, mixed fatty acids m. 58.5-59.5°, solidification point 58-56.5°, neutralization no. 201.6,
sapon. no. 204.7, I no. 47.99, nD 65 1.4397. Sepn. of liquid from solid acids gave by the Pb salt-Et2O method 54.5% solid
and 45.5% liquid acids; by the Tl2SO4 method 52.4% solid and 47.6% liquid acids; by the (AcO)2Mg method 52% solid
and 48% liquid acids. P. and A. use this method. To obtain pure stearic acid 20 g. of dried material was ground, 25 cc.
of 70% EtOH gradually added and the whole ground to a smooth paste; this was filtered on a Buchner funnel with a
hardened paper wetted with EtOH, under a low vacuum. The vacuum was then increased slightly and the cake washed
6 times with 7.5 cc. of 70% EtOH, dried on the filter as much as possible and then in vacuo for 2-3 days.
SciFinder® Page 44
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67. Constituents of the kawa root. IX. Synthesis of yangonin

By Borsche, W.; Bodenstein, C. K.; Lewinsohn, Michael
cf. C. A. 23, 2965. Yangonin may be considered as the cyclic anhydride (I, R = p-MeOC6H4CH:CH) of the Me ester of
yangonaic acid, RC(OH):CHCOCH2CO2H (II), and attempts were accordingly made to convert the ester into I by heating
with Ac2O, but MeOH was split off instead of H2O, with formation of yangonalactone (III) which under the conditions of
the expt. is at once converted into the "acetylyangonalactone" (IV), already obtained by Winzheimer. IV is deacetylated
readily, slowly by MeOH, more rapidly by dil. alkalies or by alkali carbonates. The product obtained in the last case is III,
not "acetylyangonaic acid," as W. believed. It behaves toward bases as a quite strong acid, dissolving smoothly even in
NaOAc as an α-hydroxy-γ-pyrone and not as II, for it is repptd. unchanged by dil. mineral acids and converted into I by
CH2N2 or by Me2SO4-NaOH. It was evident, therefore, that the synthesis of I would have to be effected through III. p-
MeOC6H4CH:CHCOCl was condensed with EtO2CCHNaCOCH2CO2Et to Et 3-carbethoxyyangonaate,
RCOCH(CO2Et)COCH2CO2Et (V), which with boiling Ac2O yielded, by loss of 1 mol. EtOH and simultaneous acetylation,
a mixt. of isomeric yellow acetylcarbethoxyyangonalactones, m. 104-5° (VI) and 220° (VII). VI, the chief product, is
readily deacetylated by N KOH in MeOH at room temp., while VII is repptd. unchanged by acids after standing a long
time in the alk. soln. The same difference in stability towards alkali has been observed between I, an α-methoxy-γ-
pyrone, and methysticin, a γ-methoxy-α-pyrone, and it may be therefore be assumed that VI and VII have the structures
assigned to them. It necessary to isolate VI to obtain the 3-carboxyyangonalactone (VIII). The mixt. of VI and VII is
smoothly converted by shaking with cold N NaOH in McOH into the homogeneous Et ester (IX) of VIII, and the IX with
aq. 2 N NaOH readily yields the free VIII. The decarboxylation of VIII, however, offered unexpected difficulties. This
could not be effected either by boiling the VIII with Ac2O or by heating it in glycerol or without a solvent above its m. p.;
however, on adding it to boiling PhNO2, it gave a satisfactory yield of III, identical in every respect with the product
obtained from I. The IV, m. 133°, is ordinarily obtained from II and Ac2O, but in 1 case there was obtained an isomeric
acetylisoyangonalactone (X), m. 185-6°, showing the same difference toward alkali, as compared with IV, as was found
between VI and VII; IV and X are therefore assigned the structures VI and VII (H instead of EtO2C), resp. The prepn. of
X could not be repeated even after a systematic variation of the exptl. conditions. It is deacetylated to III by 10% NaOH
only after several hrs. heating. Catalytic hydrogenation in N NaOH smoothly converts it into
acetyldihydroisoyangonalactone (XI) (X, R = MeOC6H4CH2CH2 instead of MeOC6H4CH:CH) whereas in MeOH
suspension was obtained an Ac-free dihydroyangonalactone to which is assigned the structure XII because with
Me2SO4-NaOH it gives dihydroyangonin which is degraded to p-MeOC6H4CH2CH2CO2H. Me ester of II, from II and
CH2N2 in Et2O, m. 78.5°. V (di-Et p-methoxycinnamoylacetone-α,α'-dicarboxylate.), S-yellow, m. 51-2°, was isolated
through the Cu salt, green, m. 138-40° (56 g. from 40.4 g. CO(CH2CO2Et)2). IX (2.6 g. from 3.58 g. of the mixt. of VI and
VII), seps. from hot MeOH in orange-yellow prisms on rapid, in yellow-brown rhombic tables on slow cooling; both forms
m. 149-50°. VIII (2 g. from 3.16 g. IX), light orange, decomps. 212-5°. XI, yellow, m. 107-8°. XII, m. 181-2°.
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68. An investigation of cane molasses distillery slop, with special reference to certain organic acids
By Nelson, E. K.; Greenleaf, C. A.
From Industrial and Engineering Chemistry (1929), 21, 857-9. Language: Unavailable, Database: CAPLUS,
DOI:10.1021/ie50237a015
The slop find the following analysis: solids [in vacuo at 100°] 51.22%, ash 12.65, CaO 1.78, MgO 0.47, Fe2O3 and Al2O3
0.15, Na2O 0.38, K2O 5, Mn3O4 0.015, SiO2 0.10, P2O5 0.21, SO3 0.37, Cl 2.17, N 1.43, ammonia N 0.06, amino N 0.3,
pentoses 1.11, reducing substances 4.63. The volatile acids were acetic 0.9%, formic 0.3. The non-volatile acids were
succinic 0.5%, tricarballylic about 1%, lactic 3, a small quantity of aconitic and a trace of citric. 0.6% glycerol was extd.
Attempts to identify carbohydrates by means of C6H5NHNH2, acetylation and pptn. with ammoniacal Cu were not
successful.
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69. Acetylation of starch, An investigation of the; solubility of starch

By Tsuzuki, Yojiro
From Bulletin of the Chemical Society of Japan (1929), 4, 153-6. Language: Unavailable, Database: CAPLUS
SciFinder® Page 45
Starch was acetylated in nonaq, solns.; 20 g. of starch in 30 g, of glycerol and 2 g, of ZnCli2 were heated for 15 hrs. at
170°, cooled to 70°, then 140 cc, of Ac2O was added slowly. The mixt, was heated 30 min. at 80°, and poured into H2O.
Yield 95% of triacetyl starch, m. 240-5°. Lower temps. yield incompletely acetylated products and higher temps. cause
excessive depolymerization.
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70. A new source of pure stearic acid

By Pieraerts, J.; Adriaens, J.; Meulenberg, J.
From Matieres Grasses (1929), 21, 8701-3. Language: Unavailable, Database: CAPLUS
A botanical description is given of Dumoria africana A. Chev. The wt. of the seed varies from 11.1 g. to 23.7 g. The shell
contains 12.35% moisture. The dry matter of the shell contains total ash 0.54, H2O-insol. ash 0.22, H2O-sol. ash 0.32,
total N 0.28, alkali as K2CO2 in total ash 23.32, in H2O-sol. ash 40.06%. The kernel contains 7.79% moisture. The dry
matter contains total ash 2.65, H2O-isol. ash 1.12, H2O-sol. ash 1.53 total N 1.18, P2O4 0.40, fatty matter 33.78, alkali as
K2CO3 in total ash 24.83%. The oil cake contains 1.78% N on dry basis and 0.61 % P2O5. Petroleum ether exts. 31.89,
anhyd. Et2O 1.95, CHCl2 2.84, anhyd. EtOAc 2.47, abs. EtOH 19.47%. No alkaloids or tannins are present in the kernel;
a fair quantity of saponin is present. The butter extd. by petroleum has a faint yellow color and is almost tasteless. The
consts. of cold and hot ext., resp., are d15 100 0.8914, 08890; m. p. 29.5-35°, 30-35°; solidification point 25-21.5°, 24-21°;
nD 40 1.4572, 1.4572; Crismer index 76, 74; acid index 12.44, 16.57; sapon. index 186.6, 187.4; ester index 174.16,
170.83; Reichert-Meissl index 1.16, 0.84; Polenske index -2.67; I index 47.49, 46.81; unsaponifiable 0.92, 0.93; glycerol
8.17, 8.17; sapon. index of acetylated butter 191.3, 195.2; acetyl index 6.10, 6.60; Halphen, Millian-Becchi, Beauduin, all
neg. Consts. of mixed fatty acids of the cold and the hot ext., resp., are: Hehner no. 95.45, 95.85; insol. fatty acids
94.53%, 94.92%; m. p. 53.8-54.4°, 53.5-54°; solidification point 50-48.5°, 50-47.5°; neutralization index 190.8, 191.7;
sapon. index 195, 193.8; I index 50.30, 50.60, sapon. index of acetylated acids 215.9, -; acetyl index 23.6, -; nD 60
1.4405, 1.4408; Halphen and Beauduin reactions, neg. Consts, of solid fatty acids hot extract: proportion of solid acids
46%, m. p. 62.5-64°, solidification point 61-59°, neutralization index 192.3 sapon index 197.8, I index 2.6, nD 66 1.4411.
Consts. of liquid fatty acids: proportion of liquid acids 54%, neutralization index 204.3, I index 88.2, nD 40 1.4540. The
solid fatty acids were recrystd. from, 70% EtOH and the crystals obtained possess consts. similar to those of pure stearic
acid. Exptl. data show conclusively that the butter of Dumoria africana is essentially a mixt. of the glycerides of stearic
and oleic acids; it also contains small quantities of the glyceride of palmitic acid and of an acid-alcohol. No fatty acid
higher than C18H26O2 is present. Tables are given comparing Dumoria africana with Dumoria heckcli. The commercial
value is also discussed.
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71. A new series of depolymerization products of starch

By Pictet, Ame; Vogel, Hans
Previously reported degradation products of starch are not true structural units of starch, as they show neither a color
with I nor a tendency to polymerize. Isotrihexosan (I) shows both of these properties. Dry potato starch, heated with 3
parts dry glycerol in an oil bath at 220°, dissolves gradually, and after 3 hrs. begins to show a violet color with I2. After 2
hrs. more, the mixt. is cooled, 10 parts abs. alc. added, and the ppt. washed again with alc. And purified by soln. in H2O
and repotn. with alc.; 72% of I results, a white cryst. powder, (C6H10O5)3, mol. wt. in H2O, 472 (calcd. 486). turns yellow
toward 235° m. 260-2° (decompn.) [α]D 166.4-6.7° in H2O, does not reduce Fehling soln., or neutral KMnO4, is not
attacked by emulsin. Malt diastase changes I to dextrinose (II) (synonym for isomaltose from starch, to avoid confusion
with Fischer's isomaltose from glucose), and hot dil. HCl gives glucose. Heated with 6 parts Ac2O and 3 parts (C5H5N, I
gives a nonaacetate, m. 156°, decomps. about 200°, mol. wt. in AcOH, 878 (calcd. 864), [α]D 154.8° in CHCl3; cold
NaOMe in alc. regenerates I. When I is dissolved in cold concd. HCl and the latter allowed to evap. in vacuo, a new
trisaccharide, isotrihexose, results, decomps. 155-60°, mol. wt. in H2O, 543 (calcd. 504), [α] 102.1° in H2O, reduces hot
Fehling soln. and gives no color with I2; the very sol. osazone m. 169-71°. Dil. H2C2O4 hydrolyzes I to II, crystals with
1H2O from 80% alc., m. (67-8° (dry; hydrate, m. 94-6°), mol. wt, in H2O, 338 (calcd., 360), [α]D 141.6 in H2O; osazone,
m. 167° (the osazone from II contg. 17% maltose, m. 154°; previous prepns. of II probably contained maltose).
Acetylation of II gives maltose octaacetate. When I is heated more severely (240°) with glycerol, it is further
depolymerized to dextrinosan (III), which can also be obtained from starch directly, best with the addn. of a little H2C2O4;
III. (C4H10O5)2, m. 185-6° (decompn.), mol. wt. in H2O, 305-41 (calcd. 324), [α]D 150.3-1° in H2O; best purified by
regeneration from its hexaacetate, m. 140-3°, mol. wt in C6H6, 559 (calcd. 576), [α]D 145.5° in CHCl3. Hydration of III
with cold concd. HCl gives II; but dehydration of II by heating 1 hr. at 175° and 12 mm. gives an anhydride isomeric with
III, amorphous, m. 130-40° , and assumed to contain an ethylene oxide group, since it regenerates II on boiling in H2O.
In concd. soln. in H2O, I forms (in 12-24 hrs.) a ppt. of a polymer, isopolyhexosan (IV); light does not affect the change,
which in inhibited by various salts. IV forms rather starch-like grains which show birefringence, softens 235° and
decomps. 245°; boiling with H2O reforms I, and hydrolysis with HCl gives only glucose. Acetylation of IV gives
(C6H7O6Ac2)13, [α]D 177.4° in CHCl3, mol. wt. in C6H6, 3325, 3411 (calcd. 3458).
SciFinder® Page 46
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72. A crystallized acetin and diglyceride

By Battegay, M.; Buser, H.; Schlager, E.
Anhyd. glycerol (120 g.) and 200 g. of HOAc were heated below 135° with 2 g. of H2SO4 (66 Be.), distg. off the H2O as
formed; the HOAc was replaced 3 times in 20 cc. portions at 8-hr. intervals. Fractionation in vacuo gave 3 fractions; 40
g. b14 140-60°; 30 g. b14 160-90°; 10-20 g. b14 190-250° and a residue of 30-10 g. The 2nd fraction gave 4-8 g. of
crystals, which were recrystd. from H2O and found to be diglyceryl diacetate (I), C7H14O2(OAc)2, m. 179° (cf. Rangier, C.
A. 22, 4168). Boiling I in EtOH with HCl for 1 hr. and evapg. the EtOAc, EtOH and HCl gave diglycerol (II), C6H12O4, b14
173°, m. 96-7°. Acetylation of II gave I; benzolation gave the dibenzoate, m. 138°, and fusing II with PCl3 gave diglyceryl
dichloride, m. 112°. II is either HOCH2CH.CH2.O.CH(CH2OH).CHub2.O or HOCH2CH.CH2.O.CH2.CH(CH2OH).O.
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73. The chemical structure of the associated components obtained from gelatin and from gelatin peptone. VIII.
The nature of the acetylated peptide associations obtained from gelatin decomposed by glycerol
By Fodor, A.; Epstein, Ch.
From Biachem. Z. (1930), 228, 315-26. Language: Unavailable, Database: CAPLUS
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74. Synthesis of 2-glycerol d-glucoside

By Carter, Neal M.
In an unpublished investigation with Bergmann it was found that 1,3-benzylideneglycerol (I) affords an excellent means of
prepg. 2-glycerides; the 2-HO group is acylated and then the PhCH residue is split off with catalytically activated H. In
this way were prepd. 2-benzoylglycerol, m. 72°, and 2-glycerol glucoside (II). With acetobromoglucose, I yielded 1,3-
benzylidene-2-[tetraacetylglucosido]glycerol (III), which was deacetylated to the 1-glucosido compd. (IV) and the IV on
catalytic hydrogenation gave II quantitatively. II readily seps. in well-formed crystals of sweet taste, m. 166° (cor.), [α]D 20
-30.1° (H2O). It is readily hydrolyzed by emulsin (85% in 2 hrs. at 18°), which shows that it is a β-glucoside and
distinguishes it from the compd. (V) obtained by Karrer and Hurwitz from 1,2-acetoneglycerol and acetobromoglucose.
The hexaacetate (VI) of II m. 128°, [α]D 20 -14.9° (CHCl3), [α]D 19 in (CHCl3)2; that of V m. 98°, [α]D 15 -31° (alc.). The 2
acetates are entirely different; thus, VI is so difficultly sol. in alc. that it was not possible to prep. a 1% alc. soln. for
polariscopic measurements. K. and H. concluded from the rotation (-27.7°) of their non-cryst. V that it is identical with the
cryst. product (-28.2°) of Bourquelot and co-workers, prepd. by enzymic synthesis, but in view of the very similar rotation
(-30.1°) of II and the indefinite m. p. (130-5°) of B.'s cryst. compd. N. feels that the nature of B.'s compd. has not yet been
established. To det. whether the glucose residue in II readily migrates to the 1-position under the influence of dil. acids,
the PhCH group in III was split off in 1 expt. with dil. HCl, in another by catalytic hydrogenation. In the latter, 2-
[tetraacetylglucosido]glycerol (VII) was readily obtained in well-crystd. form and in quant. yield, whereas with HCl the
product was a sirup, as, in spite of careful work, some Ac was split off along with the PhCH. No migration of the glucose
residue occurred, however, as shown by the ready acetylation of the product to VI. III (38% yield), m. 133° (cor.), [α]D 20 -
34.2° (CHCl3). IV (88% from IV with NH3MeOH), seps. from C6H6-EtOH in crystals m. 138°. Air-dried, it loses 5.7% in
wt. under 0.1 mm. over P2O5 at 100°, changing, with effervescence, into a glassy mass which liquefies 85-95°, solidifies
around 110° and again m. 155-62°, [α]D 20 -18.5°. VII, m. 103° (cor.), [α]D 19 22.1° (H2O), 3.3° (CHCl3).
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75. Synthesis of β-glycerides

By Bergmann, Max; Carter, Neal M.
From Z. physiol. Chem. (1930), 191, 211-21. Language: Unavailable, Database: CAPLUS
SciFinder® Page 47
β-Monoglycerides of fatty acids have not hitherto been prepd. A method is now described in which the cyclic α,α'-
benzalglycerol is acylated on the β-OH and then the benzal group removed by catalytic hydrogenation. The yield of β-
glyceride is 80% or better. The mixt. of isomeric benzalglycerols obtained by condensation of glycerol with BzH was
treated with dry HCl in the cold to rearrange the α,β'- into the α,α'-form and a 90% yield of the latter was thus obtained.
The product can be purified by sublimation. Its β-Bz deriv. was hydrogenated in EtOH with Pd catalyst and evapd. in
vacuo to crystn., yielding 98% of β-benzoylglycerol, m. 72.5°. The latter can be condensed again with BzH to form the
original substance. A similar condensation can be made with MeAc in the presence of CuSO4, yielding 80% of β-
benzoyl-α,α'-isopropylideneglycerol, m. 33°. When this is mixed with the isomeric α-benzoyl-α',β-isopropylideneglycerol,
m. 34.5°, liquefaction occurs. Acetylation of α,α'-benzylideneglycerol (I) with Ac2O and pyridine gave 94% of β-acetyl-
α,α'-benzylideneglycerol, m. 101°. Hydrogenation converted this into β-acetylglycerol, a viscous oil, b0.3 177-8°.
Condensation of I with palmityl chloride in the presence of pyridine gave a mixt. of 2 products. The product, which was
more difficultly sol. in petr. ether, was identified as β-palmityl-α,α'-benzylideneglycerol (II), m. 63.5°. The other more sol.
substance was probably an isomeric form. Hydrogenation of II yielded β-palmityl glycerol, m. 69°. The latter may be
converted back to II by condensation with BzH. Condensation of a-palmitin gave 63% of α-palmityl-α',β-
benzylideneglycerol, m. 35°. A similar condensation of β-palmitin with MeAc gave 75% of β-palmityl-α,α'-
isopropylideneglycerol, m. 44°. When this condensation was performed in the presence of HCl and Na2SO4instead of
CuSO4a rearrangement occurred with formation of 72% of α-palmityl-α',β-isopropylideneglycerol, already described by
Fischer, et al. (C. A. 15, 684).
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76. Polysaccharides. XLIII. Effect of heating polysaccharides in glycerol

By Karrer, P.; v. Krauss, E.
cf. C. A. 24, 1538. Acetylated starch (44.7% Ac) when heated in glycerol at 200-20°for several hrs. gives. a product (1)
contg. 7-10% Ac. This shows that hydrolytic processes occur which may affect glucosidic linkages. Cu nos. of the
partially deacetylated compds. vary about 2. Yields were not quant. and the stronger reducing portions remain in the
mother liquor after pptn. with ale. I which dialyzes quickly and completely through collodium membranes is like starch (II)
in regard to its behavior with AcBr by means of which it is degraded to acetobromomaltose and then to hepta-
acetylmaltose (III) in yields about the same as that obtained from II. These results are similar to those obtained by Pictet
and Vogel (C. A. 23, 4676) by heating II in glycerol, in which isotrihexosan (IV) was formed. IV, dextrinosan (obtained by
heating II with glycerol at 240°), and dextrinose (V) (obtained by the action of H2C2O4 or malt diastase an IV) were
degraded with AcBr. The first 2 gave yields of III, about the same as that from II, but with V the yield was less. These
substances, therefore, are most correctly viewed as partially hydrolytically attacked but not yet profoundly changed
starch.
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77. o- and p-bz-Nitrochlorequinolines

By Fourneau, E.; Trefouel, M.; Trefouel, Mme.; Wancolle, A.
From Bulletin de la Societe Chimique de France (1930), 47, 738-55. Language: Unavailable, Database: CAPLUS
Of the 8 possible chloronitroquinolines in which the Cl and NO2 groups are o and p to each other in the benzene nucleus,
4 have already been described. By using Skraup's synthesis on aminonitrochlorobenzenes, 3 more have been prepd. 5-
Nitro-8-chloroquinoline (I). o-O2NC6H4Cl is reduced with Fe and AcOH and the product nitrated. To a mixt. of 14 g. of
this Cl(O2N)C6H2NH2, 11.6 g. arsenic acid, and 24 g. of glycerol is added slowly 22 g. H2SO4. After refluxing at 130° for
8 hrs. and cooling, the mixt. is poured into 10 times the amt. of H2O. Recrystd. from alc. at 96°, it m. 145°. I is also
prepd. by the conversion of o-ClC6H4NH2 by arsenic acid, H2SO4, and glycerol to o-chloroquinoline and subsequent
nitration. 5-Nitro-6-chloroquinoline (II) is prepd. by the conversion of p-O2NC6H4Cl to p-chloroquinoline followed by
nitration. The nitration of p-ClC8H4NH2, followed by Skraup's synthesis, gives a mixt. of II and 6-chloro-7-nitroquinoline
(III). 5-Chloro-8-nitroquinoline (IV). m-ClC8H4NH2 is acetylated and nitrated, and the isomers sepd. The deacetylation of
the 3-chloro-6-nitroacclanilide with 50% HCl gives 3-chloro-6-nitroaniline from which IV, m. 136°, is made by the Skraup
synthesis. The nitration of the mixture of 5- and 7-chloroquinoline, formed by the Skraup reaction starting from m-
O2NC6H4NH2, gives a mixt. of IV and 7-chloro-8-nitroquinoline, m. 186°. The nitration of m-ClC6H4NHAc gives a mixt. of
o- and p-nitro-m chloroacetanilides which on deacetylation and subsequent Skraup's synthesis yeild mixts. of 5-chloro-6-
nitroquinoline, m. 153° and 7-chloro-6-nitroquinoline, m. 155-6°.
~1 Citing

SciFinder® Page 48
78. Anhydrosugars. III. Xylosans
By Hibino, Tasuku
From Nippon Kagaku Kaishi (1921-47) (1930), 51, 417-31. Language: Unavailable, Database: CAPLUS,
DOI:10.1246/nikkashi1921.51.417
cf. C. A. 24, 5026. Xylan (I) was prepd. by washing rice straw with 2% NH4OH and then extg. with 7% NaOH, pptg. with
an equal vol. of 94% alc. and washing with alc. and Et2O. This was purified by dissolving in 4% NaOH, pptg. with alc.,
washing with 80% alc., bleaching with Cl water, then washing again with 80% alc. After acidifying with HCl, it was filtered
off and washed. The process was repeated twice. The yield was 6.3% of a white powder, m. 198°, [α]D -94.3°. The di-
Ac deriv. of I was prepd. by boiling with Ac2O, or by using Ac2O and pyridine at room temp., or by boiling with Ac2O and
ZnCl2. The mol. wt. (Barger and Rast) and values for [α]D ranged according to the method of acetylation from 400° to
633°, and -55.7° to -67.0°, resp. The prepn. of dimethylxylan was difficult. Partially methylated xylan (29% MeO, [α]D -
73.0°) was first prepd. from I and Me2SO4 in NaOH. This was converted into acetylmethylxylan (II) by Ac2O and pyridine.
II and Me2SO4 in NaOH soln. gave dimethylxylan (MeO 38%, [α]D -94.1°). By comparing the values and signs of [α]D for
cellulose and I and their derivs., H. concludes that I has the β-type constitution like cellulose and has free OH groups at
positions 2 and 3. In order to learn the nature of the basic mol. complex of I, I was heated with glycerol. A compd.
C8H14O6 (III), [α]D 42.6°, was obtained which was found to be the condensation product of xylosan (IV) and glycerol. Ac
deriv. of II, [α]D 46.7°; Me deriv., [α]D 29.5°. It is assumed that during its depolymerization, the I of β-type structure
changes directly to the IV of α-type resulting in a change in the sign of rotation. α-Xylose on distg. at 150° and 23-5 mm.
gives IV, which on heating with water yields xylose. Di-Ac deriv., [α] 35.5°. From the resemblance of the optical
properties it is concluded that the configuration of IV resembles that of glucosan.
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79. A new source of pure stearic acid

By Pieraerts, J.; Adriaens, J.; Meulenberg, J.
From Matieres Grasses (1930), 22, 8726-8,8757-8,8782-5. Language: Unavailable, Database: CAPLUS
A botanical description is given of Dumoria africana A. Chev. The wt. of the seed varies from 11.1 g. to 23.7 g. The shell
contains 12.35% moisture. The dry matter of the shell contains total ash 0.54, H2O-insol. ash 0.22, H2O-sol. ash 0.32,
total N 0.28, alkali as K2CO2 in total ash 23.32, in H2O-sol. ash 40.06%. The kernel contains 7.79% moisture. The dry
matter contains total ash 2.65, H2O-isol. ash 1.12, H2O-sol. ash 1.53 total N 1.18, P2O4 0.40, fatty matter 33.78, alkali as
K2CO3 in total ash 24.83%. The oil cake contains 1.78% N on dry basis and 0.61 % P2O5. Petroleum ether exts. 31.89,
anhyd. Et2O 1.95, CHCl2 2.84, anhyd. EtOAc 2.47, abs. EtOH 19.47%. No alkaloids or tannins are present in the kernel;
a fair quantity of saponin is present. The butter extd. by petroleum has a faint yellow color and is almost tasteless. The
consts. of cold and hot ext., resp., are d15 100 0.8914, 08890; m. p. 29.5-35°, 30-35°; solidification point 25-21.5°, 24-21°;
nD 40 1.4572, 1.4572; Crismer index 76, 74; acid index 12.44, 16.57; sapon. index 186.6, 187.4; ester index 174.16,
170.83; Reichert-Meissl index 1.16, 0.84; Polenske index -2.67; I index 47.49, 46.81; unsaponifiable 0.92, 0.93; glycerol
8.17, 8.17; sapon. index of acetylated butter 191.3, 195.2; acetyl index 6.10, 6.60; Halphen, Millian-Becchi, Beauduin, all
neg. Consts. of mixed fatty acids of the cold and the hot ext., resp., are: Hehner no. 95.45, 95.85; insol. fatty acids
94.53%, 94.92%; m. p. 53.8-54.4°, 53.5-54°; solidification point 50-48.5°, 50-47.5°; neutralization index 190.8, 191.7;
sapon. index 195, 193.8; I index 50.30, 50.60, sapon. index of acetylated acids 215.9, -; acetyl index 23.6, -; nD 60
1.4405, 1.4408; Halphen and Beauduin reactions, neg. Consts, of solid fatty acids hot extract: proportion of solid acids
46%, m. p. 62.5-64°, solidification point 61-59°, neutralization index 192.3 sapon index 197.8, I index 2.6, nD 66 1.4411.
Consts. of liquid fatty acids: proportion of liquid acids 54%, neutralization index 204.3, I index 88.2, nD 40 1.4540. The
solid fatty acids were recrystd. from, 70% EtOH and the crystals obtained possess consts. similar to those of pure stearic
acid. Exptl. data show conclusively that the butter of Dumoria africana is essentially a mixt. of the glycerides of stearic
and oleic acids; it also contains small quantities of the glyceride of palmitic acid and of an acid-alcohol. No fatty acid
higher than C18H26O2 is present. Tables are given comparing Dumoria africana with Dumoria heckcli. The commercial
value is also discussed.
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80. Some new sulfur-containing sugar derivatives

By Gehrke, Max; Kohler, Walter
From Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen (1931), 64B, 2696-702.
Language: Unavailable, Database: CAPLUS
SciFinder® Page 49
The series of thioses (sugar derivs. in which the 1-HO group is replaced by SH) has been extended by the prepn. of the
arabinose, xylose, glycerol and glycolaldehyde compds. The rhamnose compd. could not be obtained. Instead of the
expected acetylated thio deriv., there was obtained triacetylmethylrhamnoside, evidently formed by reaction of the
acetobromorhamnose with the solvent MeOH, but in other alcs. also (Et, Bu, Am) only S-free products were obtained.
Dixylosyl disulfide hexaacetate (I) (11 g. from 34 g. acetobromoxylose (II) and a soln. of 4 g. K in 160 cc. MeOH satd.
with H2S at 0° and contg. 1.6 g. pptd. S in soln.), m. 142°, [α] D 23 -254.6° (CHCl3), hydrolyzed by NH3 in MeOH at 0° to
dixylosyl disulfide, m. 188-91° (decompn.), seps. with 1 H2O, [α]D 20 -283.6° (water). Tetraacetylxylothiose (III) (10 g.
from 15 g. II boiled 5 min. with 6 g. AcSK in EtOH), m. 99°, [α]D 24 -6.88° (CHCl3), also obtained by reduction of I with Zn
dust-AC2O-NaOAc. Triacetylxylose ethylxanthate (IV) (9 g. from 16 g. II in MeOH with EtOCS2K), m. 105-6°, [α]D 25
17.30° (CHCl3). K xylothiosate, from III or IV with K in alc., faintly yellowish, very hygroscopic, amorphous powder, m,
160° (decompn.), [α]D 20 -16.5° (water); the free xylothiose, which could not be isolated, showed mutarotation, [α]D 20
changing from-20.1° (water) 5 min. after prepn. of the soln. and to 2.4° (const.) in 20 hrs. Triacetylethylxylothioside, from
II, K and EtSH in MeOH and subsequent acetylation with Ac2O- NaOAc, m. 101°, [α]D 24 -83.5° (CHCl3), hydrolyzed by
Ba(OH)2 to Et xylothioside, m. 117°, [α]D 20 -62.8° 5 min. after soln., -78.1° (const.) after 24 hrs. Diarabinosyl disulfide
hexaacetate (yield, 34%), m. 152°, [α]D 20 -215.2° (CHCl3). Diarabinosyl disulfide (92% yield), m. 190-3° (decompn.),
[α]D 24 -228° (water). Tetraacetylarabinothiose (70-5%), m. 79°, [α]D 20 41.8° (CHCl3), Triacetylarabinose ethylxanthate,
could not be obtained in cryst. form. Na arabinothiosate (97%), prisms with 1 H2O, M. 155° (decompn.), [α]D 20 69.0°
(initial), 93.4° (final, 20 hrs.). Triacetylbenzylarabinothioside (3-4 g. from 17 g. acetobromoarabinose and 12.4 g.
PhCH2SH), m. 148°, [α]D 20 -44.6° (CHCl3); benzyl arabinothioside could not be obtained in cryst. form by sapon. with
either Ba(OH)2 or NaOMe. Diacetylglycerinothiose, from AcSK and acetobromoglyceraldehyde in boiling MeOH, m.
158°, is dimeric (mol. wt. in boiling benzene 376). Acetylglyceraldehyde ethylxanthate (yield 53%), m. 142-3°, mol. wt. in
boiling benzene 479. Na glycerothiosate, pptd. from water by alc. in prisms with 2 H2O, decomps. 230-5°. Aurous salt,
from the Na salt in aq. H2SO4 with KAuBr4, gray-green amorphous powder. Et glycerothioside, from the Na salt and EtI
in alc., m. 110°, mol. wt. in boiling acetone 265. Diglyceraldehyde disulfide, from the Na thiosate with H2O2, amorphous,
decomps. 200-5°. Acetylglycolothiose (7 g. from 12 g. BrCH2CHO and 11.5 g. AcSK.), m. 139°, mol. wt. in camphor 233.
Glycolaldehyde ethylxanthate (yield, 35%), m. 112°, mol. wt. in camphor 324. Na glycolothiosate (73.5%), prisms with 2
H2O, decomps. above 300°. Et glycolothioside (45%), m. 40-1°, mol. wt. in boiling acetone 215, is very bitter.
Diglycolaldehyde disulfide (46%), amorphous, decomps. 223-5°.
~0 Citings
81. Neutral products of oxidation of pinene

By Slawinski, K.; Piliczewski, J.; Zacharewicz, W.
From Roczniki Chemii (1931), 11, 763-73(773 in English). Language: Unavailable, Database: CAPLUS
Pinene, b. 156-7°, [α]D, -16.24°, d0 0 0.8758, nD 22 1.4647, oxidized in a 10% acetone soln. by means of 5% KMnO4
according to Wagner, gave partly oxidation products sol. in aq. acetone (I), the rest (36%) being pinene, which did not
enter into the reaction. I consisted of a fraction b3, 37-102°, which gave a compd. C10H16O2, m. 124-5°. Its
monosemicarbazone, C11H19ON3, is decompd. at 204°. Oxidation with KMnO4 or Ag2O yielded pinononic acid, m. 130-
1°. The fraction of I b2 102-116° gave a glycol, C10H18O2 (II), m. 56-7°, b1 101-2°, optically inactive. II, treated with PCl5
in CHCl3, gave as the main product a pinol, b15 76-85°. Oxidation of II with KMnO4 gave α-pinonic acid, m. 103-4°.
Furthermore, II gave a monourethan, C17H23O3N, decomps. 78°. Acetylation of II gave a mixt. of the monoacetate and
an acetate of the unsatd. alc. C10H16O. The latter was isolated by fractionating the ester mixt. and sapong. the fraction
b1, 80-5°: The alc. has a cumin odor, b1, 70-2°, d0 0 0.9757, d0 24 0.9616, nD 25 1.4913; it is oxidized by KMnO4 to a
glycerol. It is concluded that, depending on the means of oxidation, either the double bond is oxidized, yielding pinene
derivs., or the conjugated bond, yielding terpene derivs. of a 1-ring structure (cf. C. A. 19, 52).
~0 Citings
82. Acetyl determinations

By Hoppmann
From Pharmazeutische Zeitung (1931), 76, 329. Language: Unavailable, Database: CAPLUS
Reference is made to a recent paper (cf. C. A. 25, 1761) in which the advantages in the use of the Verley and Bölsing
method of acetylation were emphasized; satisfactory values are reported by this method in the examn. of EtOH, glycerol,
iso-PrOH, thymol, salol, β-naphthol, menthol and santalol. The method failed with citronella oil (geraniol).
~0 Citings
83. The thermal decomposition of inulin

SciFinder® Page 50
By Berner, Endre
From Forhandlinger - det Kongelige Norske Videnskabers Selskab (1932), 5, 167-70. Language: Unavailable,
Database: CAPLUS
The expts. of Vogel (C. A. 24, 1626), and V. and Pictet (C. A. 22, 4480), on heating inulin with glycerol, were repeated by
B., leading to the conclusion that the thermal decompn. produced is based upon an alcoholytic process as found with
lichenin. The reaction which yields glycerol glucosides of the decompn. products is formulated as follows:
.sbd.O.CH.O.CH.sbd. + HOC3H5(OH)2 → .sbd.O.CH.O.C3H5(OH)2 + HOCH.sbd.. Procedure: 20 g. dried inulin and 30 g.
distd. glycerol are heated in vacuo to 140° for 6 hrs. The ppt. (I) after soln. of the reaction product in MeOH and addn. of
Et2O and the fractions (II) and (III) obtained after evapn. of the solvents and pptn. from MeOH-acetone were purified and
tested as to [α] in C6H6, glycerol content according to Zeizel-Fanto, Ac content with alc. KOH and the mean no. of
C6H10O5 groups for calcn. of the mol. wt. The removal of the glycerol is effected by acetylation and that of the triacetin
constituent partly by evapn. in a high vacuum and partly by repptn. from MeOH-H2O. The results ([α]D, % glycerol
content, % Ac content, av. no. C6H10O5 groups, resp.) obtained for the purified acetates were: I, -12.4°, 2.59, 45.9, 11.5;
II, -5.0°, 3.62, 46.1 (calcd. 46.03), 8.5; III, 21.6°, 12.8, 49.2 (calcd. 49.16), 1.8 (mol. wt. in C6H6 650; calcd. 718). I and II
were white powders and III was a vitreous substance. The alc. fraction produced by prolonged alcoholysis had a glycerol
content of 14.8%, Ac 49.8% (calcd. 49.85), C6H10O5 groups, 1.44. The 80% of this product not used for analysis, after
simultaneous deacetylation and methylation with Me2SO4 and NaOH and distn., gave a completely methylated water-
clear liquid glycerol fructoside b. 125° with [α]D 20.8°, mol. wt. 340, Ac content 0.58%, and the probable formula
O.CH2.CH(OH).CH(OH).CH(OH)C-[OC3H5(OH)2]CH2OH. The possibility of a rearrangement simultaneously occurring
with alcoholysis is mentioned.
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84. Quantitative examination of salve bases

By Csipke, Zoltan
From Magyar Gyogyszeresztudomanyi Tarsasag Ertesitoje (1932), 8, 49-55. Language: Unavailable, Database:
CAPLUS
In the evaluation of ointments (1) glycerol should be detd. to show the content of oils or other triglycerides, (2) unsatd.
acids should be detd. to identify the triglycerides, (3) total unsaponifiable matter should be detd. to give the content of
wax, lanolin, spermaceti, solid or liquid paraffin or vaseline, etc., and (4) the wax alcs. of the unsaponifiable portion
should be acetylated in order to sep. wax and paraffin components.
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85. Glycogen. II. Methylation and acetylation

By Hughes, G. K.; Macbeth, A. K.; Winzor, F. L.
From Journal of the Chemical Society (1932), 2026-31. Language: Unavailable, Database: CAPLUS,
DOI:10.1039/jr9320002026
cf. C. A. 18, 3175. Methylation of glycogen in NaOH with Me2SO4 in the absence of Me2CO, even after 25-30
treatments, gave a product contg. only 41.5% MeO, which accounts for some 8 out of every 9 HO groups; repeated
methylation in the presence of Me2CO gave a product with 44% MeO. Over 75% of the theoretical amt. of
trimethylmethylglucoside was isolated after hydrolysis of this methylated glycogen but the conversion cannot be
expressed on a quant. basis in view of the fractionation necessary on account of the presence of the di-Me compd.
Glycogen or its methylated products have not been depolymerized by heating with glycerol. Potato starch was
acetylated very slowly, approx. 80% remaining unchanged after 6 days' shaking. A sample obtained by grinding the
starch with H2O to a smooth paste, boiling 0.5 hr. and pptg. by EtOH (called "treated" starch) goes into soln. in about 1
day. Wheat starch (untreated) and corn starch (treated) were acetylated in 1 day. Rice, wheat and corn starch
(untreated) dissolved in the acetylating mixt. more slowly than the treated materials but were almost completely dissolved
after 3 days. Glycogen (untreated) went into soln. in less than a day; a treated sample remained undissolved after 6
days and another had only partly dissolved even after 19 days. All of the samples of EtOH-sol. triacetate may be quant.
converted into Me glucoside. Other differences between starch and glycogen are discussed.
~1 Citing
86. Glycerol degradation of lichenin

By Berner, Endre
From Justus Liebigs Annalen der Chemie (1932), 500, 52-61. Language: Unavailable, Database: CAPLUS
SciFinder® Page 51
Lichosan, obtained by heating 8 g. lichenin with 100 g. anhyd. C3H5(OH)3 1.5 hrs. at 240° contains about 3.5%
C3H5(OH)3; that this is a part of the mol. is indicated by its presence after acetylation and regeneration of lichosan. The
regenerated product may also contain some EtOH; 1 sample is calcd. as 94.1% C6H10O5 + 3.6% C3H5(OH)3 + 2.3%
EtOH; [α]D 20 38°; mol. wt. 2800 (this value varies from 2400 to 2800).
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87. Benzyl compounds of α-hydroxy acids and their use in synthesis. I. Derivatives of glycolic acid
By Fischer, Hermann O. L.; Gohlke, Bruno
Attempts to prep. ester-like compds. of α-HO acids by the aid of carbomethoxylated α-HO acid chlorides failed, in that,
even in dil. NH3 solns., the difference between the resistance to hydrolysis of the protecting group and the depside
linkage was not sufficiently great to prevent total cleavage and consequent regeneration of the starting materials. By
employing the acid chlorides of O-benzylated HO acids and by removing the PhCH2 group by catalytic hydrogenation in
the presence of Pd (C. A. 26, 2704) various esters of glycolic and other HO acids have been prepd. which may have biol.
significance. To 20 g. Na in 400 cc. warm PhCH2OH was added gradually 40 g. ClCH2CO2H in 30 cc. PhCH2OH and the
mixt. was heated at 150° for 4 hrs. After concn., extn. with Et2O, and acidification with concd. HCl the freed acid was
extd. with Et2O. The dry ether soln. was evapd. and on fractionation at high vacuum gave 53 g. (75%) of benzylglycolic
acid (I), C9H10O3, b0.2 136°. Treatment of 15 g. of I in CHCl3 with 20.7 g. PCl5 and removal of the solvent and excess
reagent produced a crude product which was distd. rapidly at high vacuum and yielded 13 g. (78%) of benzylglycolyl
chloride (II), C9H9ClO2, b0.2 81°, anilide, C15H15NO2, m. 49°. Two g. glycolic acid in 20 cc. dry CHCl3 was shaken in the
cold with 1.1 mols. of PhNMe2 and 1 mol. of II and stood for 24 hrs. at room temp. After washing, drying and removing
the CHCl3 the neutralized AcMc soln. of the product was extd. with Et2O and acidified with concd. HCl. The dried ether
soln. was evapd. and on fractionation gave 2.15 g. (36%) of benzylglycolylglycolic acid (III), C11H12O6, b0.05 151°, m. 59°.
One g. Pd catalyst (C. A. 14, 1338) suspended in 10 cc. glacial AcOH contained in a shaking duck was satd. with H and
1.68 g. of III in 30 cc. glacial AcOH was introduced. The material absorbed 182.2 cc. of H (calcd. for H2, 183.3 cc.) at
761 mm. and 18°. The reduced material was filtered, freed from AcOH and yielded 0.8 g. (80%) of thick prisms of
glycolylglycolic acid, C4H5O5, m. 97-9° (Ann. 312, 146(1900)). A similar catalytic reduction of 1 g. of monobenzylglycolyl-
β-diacetonefructose, prepd. from II and β-diacetonefructose (C. A. 24, 3757), produced 0.6 g. (77%) of monoglycolyl-β-
diacetonefructose, C14H22O8, m. 128°. Similarly were produced α-glycolylglycerol, triglycolylglycerol,
triglycolylmonoacetoneglucose, triglycolylglucose and pentaglycolylglucose but only in an oily or amorphous state.
These compds. were estimated either by an alkalimetric detn. of the introduced glycolic acid residue or by the formation
of definite derivs. by the complete acetylation or benzoylation of the poly-HO combination product.
~2 Citings
88. Ascaryl alcohol

By Schulz, Fr. N.; Becker, Max
From Biochemische Zeitschrift (1933), 265, 253-9. Language: Unavailable, Database: CAPLUS
Ascaryl alc., obtained from the fat of ascarids, has the compn. C33H68O4 (Flury's formula is C32H64O4), as detd. by
elementary analysis and mol.-wt. detns. and from the fact that glycerol is part of its mol. constitution, accounting for the
uneven C no. No double bond was demonstrable; the alc. can be acetylated and benzoylated, yielding a diacetate m.
52° and a dibenzoate m. 37°, the m. p. of the pure alc. being 84°. Pure prepns. were obtained by sapon. of the
diacetate, but the alc. can also be obtained from the total fat by a process of fractionation. On heating at a high temp. the
development of the pungent fumes of acrolein is obvious, but the combination with the glycerol is not ethereal since it can
not be hydrolyzed by sapon.
~0 Citings
89. Alcoholytic degradation of starch

By Berner, Endre; Melhus, Fredrik
SciFinder® Page 52
It had been shown (C. A. 27, 4780) that the degradation of carbohydrates such as lichenin, inulin and sucrose by heating
with glycerol (I) or other alcs. consists in an alcoholysis, and it has now been found that the same is true of starch. The
degradation products are therefore mixts. of glucosides of the alc. used. A "trihexosan" prepd. according to Pictet and
Jahn (C. A. 17, 270) contained around 4% bound I. Complete degradation of starch with I at 180° gave a mixt. of α- and
βglyceryl d-glucosides with [α] 60°, characterized by acetylation with C5H5N-Ac2O to an acetate, [α]D 20 56.9° (benzene,
c 0.9), with 18.0% I and 50.9% Ac, which, treated twice with Me2SO4-NaOH, yielded a hexamethylglycerylglucoside, b0.1
127°, [α]D 20 59.9° (CHCl3, c 1.2), mol. wt. 284 in freezing benzene, 296 in boiling ether; this with 2 N HCl on the water
bath gave 2,3,4,6-tetramethylglucose, m. 83°, [α]D 20 in water (c 1.6) 94.5° after 12 min. and 83.2° after 48 hrs. With I at
210°, some water was split off, as evidenced by the low Ac content of the acetate (47.95%) as compared with the I
content (18.35%). On the other hand, alcoholysis was effected with I at 130° when a little H3PO4 was added as catalyst.
Starch with glycol, freed from water by heating in vacuo until 5% of the glycol had distd. off and then heated 24 hrs. at
180°, gave in good yield a mixt. of α- and β-glycolyl glucosides whose pentaacetate, b0.07 184°, showed [α]D 20 70.0°
(benzene, c 1.0); after 1 month the α-form sepd. in needles, m. 66°, [α]D 20 143.0° (benzene, c 1.4), 123.3° (alc., c 1.2),
Ac 49.62%, mol. wt. 419 in freezing benzene, 417 in boiling ether. Methylated starch, with 39% MeO and [α] 186°,
heated 11 hrs. at 200° with MeOH in a sealed tube under N yielded 2,3,6-trimethyl-(α + β)-methylglucoside, b0.04-0.05
115°, nD 1.4585, [α]D 20 60.8° (water, c 1.3), Ac 52.55%, mol. wt. in freezing water 224. Starch heated with PhOH or
PhCH2OH is alcoholyzed; PhOH and PhCH2OH can be detected in the degradation products purified through the
acetates; the Ac content and rotation correspond to extensive degradation.
~1 Citing
90. Thermal degradation of glycogen

By Berner, Endre; Dahl, Ole Gyth
From Forhandlinger - det Kongelige Norske Videnskabers Selskab (1934), 6B, 130-3. Language: Unavailable,
Database: CAPLUS
Glycogen heated in glycerol at 160° and 20 mm. pressure reached a const. rotation in 76 hrs. The glycerol was then
distd. off in vacuo and the residue acetylated, giving 82.5% of hexaacetylglycerolglucoside (I). Subsequent deacetylation
and methylation of I by 30% NaOH and Me2SO4 gave hexamethylglycerolglucoside, [α]D 20 59.0° (5.4% in CHCl3). On
hydrolysis, 2,3,4,6-tetramethyl-α-glucose was obtained, m. 84°, [α]D 20 100° (initial), 83.7° (final) (2.3% aq.). In the
presence of 2% H3PO4 the alcoholysis proceeded to 88% yield in 20 hrs. at 130° i. e., H3PO4 catalyzes the reaction. In
glycol, the alcoholysis was not complete in 48 hrs. at 180°, but an impure pentraacetylglycolglucoside was obtained. The
thermal degradation of glycogen in glycerol is therefore, as with lichenin, inulin and sucrose, an alcoholysis (cf. Berner,
C. A. 27, 1329, 4780, 5310).
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91. Reactions relating to carbohydrates and polysaccharides. XLVI. Structure of the cellulose synthesized by the
action of Acetobacter xylinus on fructose and glycerol
By Barsha, J.; Hibbert, H.
From Canadian Journal of Research (1934), 10, 170-9. Language: Unavailable, Database: CAPLUS,
DOI:10.1139/cjr34-014
cf. C. A. 25, 3969. Membranes synthesized by Acetobacter xylinus on fructose and on glycerol have been shown by the
recognized methods of methylation, acetylation, acetolysis and hydrolysis to be chemically identical with cotton cellulose.
This is confirmed by x-ray analysis. The x-ray investigation by Sisson and Clark (cf. C. A. 27, 5963) indicates the identity
of the cellulose membranes from glucose, fructose, glycerol, sucrose, galactose and mannitol by the action of A. xylinus
and thus supports the view that the same polysaccharide is synthesized by the organism whenever cell-wall formation
(growth) occurs and that this polysaccharide is chemically identical with cotton cellulose.
~2 Citings
92. d-Glucosaccharosonic acids. III. The phenylhydrazine compounds

By Ohle, Heinz
SciFinder® Page 53
cf. C. A. 28, 3715.4. As in the study of the o-C6H4(NH2)2 compds., the dehydration product, d-2,3-diketogluconic acid (I),
of d-glucosaccharosonic acid (II), rather than II itself, was used in the present work. Only the salts of I and the free acid
react readily with PhNHNH2 to form osazones; the lactone gives water-insol. condensation products in far poorer yields.
Three such products have thus far been isolated: the bis(phenylhydrazone) (III) of I, the lactone (IV) of III, and 1-phenyl-
3-(d-erythroglyceryl)-4-benzeneazopyrazole (V). The relative yields depend on the exptl. conditions; in the presence of
mineral acids (HCl), III and IV are the main products but in AcOH III is obtained in only very small amt. or not at all while
more V is formed. III on recrystn. from acetone, AcOEt or pyridine changes in great part into IV, while dil. NaOH
catalyzes the formation of V even at 20°. IV, unlike III and V, is insol. in cold dil. alkali but rearranges into V with boiling
dil. NaOH. The 3 alc. HO groups of V can be demonstrated by acetylation but the enolic HO group of the pyrazole ring
does not react even with boiling AC2O. The triacetate (VI) can be methylated with CH2N2; the Me deriv. (VII), however,
has been obtained only in resinous form, but its deacetylation product, 1-phenyl-3-(d-erythroglyceryl)-4-benzeneazo-5-
methoxypyrazole (VIII), obtained either by cautious sapon. of VI or methylation of V with CH2N2, crystallizes well. The
presence of the PhN2 group in V is shown by reductive cleavage to PhNH2 or BzNHPh with SnCl2-HCl. The other
component, 1-phenyl-3-glyceryl-4-aminopyrazolone, has thus far not been isolated in cryst. form as such or as a salt or
other deriv.; in the air it changes, in even faintly acid soln., into a red amorphous deriv. of rubazonic acid. The pyrazole
system in V can be dissected out by oxidation of VIII with KMnO4 in acetone, which gives in moderate yield 1-phenyl-4-
benzeneazo-5-methoxypyrazole-3-carboxylic acid (IX). IX dissolves in cold dil. alkalies but is repptd. by CO2. That it is
really a carboxylic acid and not a pyrazolone is shown by the following facts: (1) With excess of NaOH-MeOH it gives 1-
phenyl-4-benzeneazopyrazolone-4-carboxylic acid (X); (2) synthetic X with CH2N2 gives the Me ester of IX, which is
smoothly hydrolyzed to IX by 1 mol. NaOH; (3) the Me ester of X (prepd. with MeOH-HCl) differs from IX in its much
darker (reddish yellow) color, much lower m. p., and greater soly. With acetone and concd. H2SO4 as catalyst, V forms a
monoacetone compd. (XI) insol. in cold dil. alkalies. XI still contains 1 acetylizable alc. HO and the enolic HO group of
the pyrazole ring but no longer reacts with Ph3CCl in pyridine, while X forms an (amorphous) trityl compd. which yields
no cryst. compd. with acetone-H2SO4 but with acetone-CuSO4 gives XI, with loss of the Ph3C group. The purification
and identification of IV offers considerable difficulty. It does not crystallize readily and it retains solvent of crystn. quite
firmly. Moreover, it apparently can exist in 2 desmotropic modifications whose direct sepn. it has thus far not been
possible to effect, but acetonation yields 2 compds. (XII) differing in color-chiefly alizarinred needles and, from the mother
liquors, brown-yellow needles. They have the same m. p. and mixed m. p. and both are insol. in cold aq. NaOH but
dissolve in cold alc. NaOH with deep red color and change into XI on boiling. The Me2C group must therefore occupy
the same position in XII as in XI, but as XII can no longer be methylated, the free HO group of XI must, in XII, be in a
lactone form. IV is formed as chief product along with III and V, when II is boiled in alc. with a large excess of PhNHNH2.
Acetonation of the crude product gives chiefly IX. III gives the same products, but in poorer yields. Ascorbic acid (XIII),
the stereoisomer of II, behaves like II toward PhNHNH2. The acid corresponding to III could not be isolated because of
lack of material. The lactone osazone (XIV) analogous to IV gives with alkali 1-phenyl-3-(l-threoglyceryl)-4-
benzeneazopyrazolone (XV) which has a m. p. and rotation very close to those of V and does not depress the m. p. of V,
but its acetone deriv. (XVI) is different from XI. III, yellow needles decompg. 159-60°, [α]D 20 241° → -92° (c 2.159,
pyridine), 107.8° → 119.2° (c 2.0848, 0.2 N NaOH), loses CO2 (but considerably less than 1 mol.) at 159-60°. IV, yellow
needles from acetone, changing at 100° in vacuo to a red powder m. 202-3° (slight decompn.), [α]D 20 -93.5° (c 2.00,
pyridine), does not reduce Fehling soln. even on boiling or after treatment with concd. HCl. XII (2 forms), m. 224-5°. V,
yellow, m. 215-16° (slight decompn.), [α]D 20 -53.1° (c 1.544, pyridine), 1305° (c 0.360, 0.08 N NaOH), does not reduce
Fehling soln. and is stable to both boiling alkalies and concd. HCl; Na salt, yellow needles with 2 H2O from alk. water, m.
131-2°, [α]D 21 1054°, brownish crystals with 1 H2O from acetone, m. 187-91°, [α]D 20 1125°. XI, dark yellow, m. 181-2°,
[α]D 22 -73.8° (pyridine, c 1.246); Na salt, light yellow hydrated needles, m. (air-dried) around 100° (foaming), loses all but
0.5 mol of the H2O of crystn. in vacuo over CaCl2 and then sinters about 170°, slowly decomposes around 200°; Me
ether, from XI refluxed with MeI-Ag2O, light yellow, m. 137-8°, [α]D 18 475.6° (benzene, c 1.211), insol. in boiling dil.
NaOH, showing that the MeO group is on the pyrazole ring; acetate, m. 152-3°, [α]D 20 -14.22° (benzene, c 0.984), sol. in
much cold dil. NaOH and is hence acetylated on the glycerol side chain. VI, yellow, m. 109-10°, [α]D 20 37.6° (CHCl3, c
1.490), 54.4° (pyridine, c 2.116.), 74.2° (benzene, c 1.065). VIII, light yellow, m. 165-6°, [α]D 20 672°- (pyridine, c 1.083).
IX, m. 180-1°; Me ester, m. 133-4°. Me ester of X, m. 136.5-7.5°. 2,3-Diketo-l-idonic bis-(phenylhydrazone) lactone
(XIV), red, m. 212-14° (decompn.) (cf. Hirst et al., C. A. 28, 107.1), insol. in cold dil. NaOH but sol. in boiling alkali with
yellow color. XV, yellow flocks, m. 210-11° (decompn.), [α]D 20 1155° (0.2 N NaOH, c 0.1688) ; XVI, dark yellow, m. 170-
1° (mixed m. p. with XI, 163-5°), [α]D 25 -31.3° (pyridine, c 0.990).
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93. The hydrolysis of glycogen by glycerol extract of muscle

By Carruthers, Albert; Lee, Wei Y.
cf. Sahyun and Alsberg, C. A. 26, 485. The products of the action of the glycerol ext. of rabbit muscle on glycogen were
examd. for the presence of the trisaccharide reported by Barbour (C. A. 24, 633.). After acetylation the bulk of the
product had a mol. wt. of 600-760, i. e., corresponding to a disaccharide. However, one fraction appeared to be a higher
polysaccharide. The Ac content of most fractions was also nearly that of an acetyldisaccharide. Since the products were
not pure compds. the evidence is not conclusive but the trisaccharide, if it occurs at all, is certainly not the main product
of hydrolysis.
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94. Report of the glycerin-analysis committee of the American Oil Chemists Society
By Andrews, J. T. R.
From Oil and Soap (Chicago) (1935), 12(No. 5), 90-1. Language: Unavailable, Database: CAPLUS,
DOI:10.1007/BF02636657
Ames devised a modification of the I. A. M.: After acetylation the reaction mixt. is brought to room temp. before addn. of
the 50 cc. of H2O, and the soln. is then immediately chilled, filtered and washed with chilled H2O, and the vol. brought up
to 300 cc. Neutralization is made at once with a 25- and a 100-cc. buret, the latter with a free-flowing tip. The approx.
amt. of alkali should be calcd., and 90% of it added rapidly from the large buret; the final end point is detd. with the small
buret. The balance of the analysis is made as in the standard method. Hydrolysis of triacetin in AcOH is a very likely
source of error in the I. A. M. This hydrolysis may be reduced by chilling in ice-H2O. The end point is difficultly detd.
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95. Esterification
By Graves, Geo. D.
CAPLUS
Glycerol or glycol or one of their derivs. still contg. at least one OH group is brought into contact with a ketene (as in the
production of acetylated phenol from ketene and PhOH) in the presence of a strong acid catalyst such as H2SO4.
Several examples are given.
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96. Carvacrol. V. Benzyl ethers of acetylated methylisopropylphenols

By John, Hanns; Beetz, Paul
From Journal fuer Praktische Chemie (Leipzig) (1935), 144, 49-53. Language: Unavailable, Database: CAPLUS
cf. C. A. 29, 7958.8, p-Acetothymol (I) and PhCH2Cl with EtOH-KOH give about 85% of p-acetothymyl benzyl ether, m.
71°; p-propionyl homolog, m. 64°; p-butyro homolog, m. 47°; p-isovalero homolog, m. 40°; p-acetothymyl 4-nitrobenzyl
ether, pale yellow, m. 104°; p-propionyl homolog, pale yellow, m. 110°; p-butyro homolog, yellow, m. 97°; p-isovalero
homolog, yellow, m. 84°; p-benzoyl homolog, yellow, m. 91°. p-Acetocarvacryl benzyl ether, m. 64°; 4-nitrobenzyl ether,
yellow, m. 114°; p-propiocarvacryl 4-nitrobenzyl ether, yellow, m. 128°. I and CH2(CH2Cl)2 with EtOH-KOH give glycerol
α,α'-bis(p-acetothymyl) ether, m. 109°; the o-nitro-p-acetothymyl ether, m. 95°.
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97. Preparing cellulose for conversion into derivatives such as cellulose acetate
By Richter, Geo. A.; McKinney, James W.
CAPLUS
Cellulosic material such as sulfite wood pulp is prepd. for conversion such as acetylation by refining it in an alk. liquor
such as a soln. of NaOH and mixing it with a dil. sq. soln. of glycerol or the like.
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98. Esters of polyalcohols

By Lawson, M.
SciFinder® Page 55
Esters which are useful as plasticizers for cellulose derivs. (cellulose triacetate) and natural or artificial resins are prepd.
by (1) peracylation of an unsatd. alc., then esterification of the mono-ester thus obtained by a monoacid, e. g., treatment
of oleic alc. by peracetic acid to obtain the monoacetate of octadecanetriol, which by final acetylation gives the triacetate,
or (2) hydroxylation of alcs. of several double bonds, such as linoleic alc., followed by esterification or (3) by addn. of
HOCl to an unsatd. alc. followed by treatment with acid anhydride and AcONa to obtain the polyacetate.
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99. The treatment of glycerol by the V. Boulez method of acetylation in dilution in inactive media. The possibility
of its application to products containing less than 50% glycerol
By Boulez, Victor
From Industrie Chimique Belge (1937), 7, 439-42. Language: Unavailable, Database: CAPLUS
The method described in C. A. 27, 3164 is superior to the official methods. It can be applied to solns. contg. less than
50% glycerol and avoids the undesirable inaccuracies of the usual methods.
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100. The fatty oil of the seeds of Onguekoa gore Engler

By Steger, A.; van Loon, J.
From Fette und Seifen (1937), 44, 243-6. Language: Unavailable, Database: CAPLUS, DOI:10.1002/lipi.19370440608
The oil of Onguekoa gore Engler (also known as Ongokea klaineana) has an orange color, a greenish fluorescence and
the following consts.: d4 78 0.9337, d4 20 0.9838, nD 70 1.4903, nD 20 1.5098, sapon. no. 187, Ac sapon. no. 247, Ac no.
69, acid no. 21.1, Reichert-Meissl no. 0.37, viscosity (Vogel-Ossag; Höppler) 11.76 poises. The detn. of unsatn. gave
the following results: thiocyanogen value 51.9, 70.0, 79.9 after 24, 48 and 72 hrs., resp., Wijs I no. 103, 196, 221, 233,
232 after 5 min., 1, 7, 24 and 48 hrs., resp., Kaufmann bromometric I no. 117, 149, 209, 219, 221 after 15 min., 1, 7, 19
and 72 hrs., resp., hydrogenation I no. of acetylated oil 280, equiv. to a value of 316 for the unacetylated oil. Since acid
radicals with conjugated double bonds can scarcely be present to any extent, these results suggest the possibility of
radicals contg. triple bonds. This was confirmed as follows. The mixed Et esters (I) of the fat acids were prepd. and the
fraction distg. 115-130° under high vacuum was brominated. A hexabromide (probably that of 9, 12, 15-linolenic acid)
was isolated; the residue after debromination and distn. had the consts.: d4 78 0.8766, nD 70 1.4538, I no. (Wijs-after 2
hrs.) 166, hydrogenation I no. 247. Ozonization of the fat acids of the 115-130° ester fraction produced some azelaic
acid, plenty of adipic acid and pelargonic acid as the sole water-sol. monocarboxylic acid. It is concluded that an
acetylenic acid is present having the formula CH3(CH2)C≡CCH2CH:CH(CH2)COOH or
CH3(CH2)CH:CHCH2C≡C(CH2)COOH. From the fraction of I distg. 130-140° and acid m. 38-9° and having nD 70 1.4860
was isolated; this acid had an I no. corresponding to 3, and a hydrogenation I no. corresponding to 5 double bonds. This
acid apparently contains 1 double and 2 triple bonds. Hydrogenation of I under mild conditions, distn. of the resulting
mixt. and crystn. of certain fractions from alc. led to isolation of (1) stearic acid and (2) a hydroxylated acid (m. 75-8°)
which was difficult to purify by recrystn. from petr. ether and which was apparently a monohydroxystearic acid not
identical with the acid obtained by hydrogenating ricinoleic acid. Onguekoa oil contains 2% satd. acids, 90.3% unsatd.
acids, 1.1% unsaponifiable, 3.5% glycerol, 3.1% volatile and insol. The residue left after extn. of the oil from the nut
kernels contains 45.2% protein but is too poisonous for use for feeding stock.
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101. Glycerol lactate triacetate

By Lock, Ritchie Hart
This plastifier for cellulose derivs. is made by acetylating all the OH groups of glycerol lactate (I), which may be prepd. as
described in Brit. 456,525 (C. A. 31, 2231.8). As an example, I is acetylated with glacial ACOH in presence of H2SO4
and C6H6; the C6H6 for the distillate is sepd. and returned to the reaction vessel until the required quantity of H2O is
removed.
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102. Films and foils
Cellulose ester foils or films are obtained by producing 1 film by a wet-casting method and then casting 1 or more further
films upon the 1st film by wet casting so as to obtain composite films. Preferably, the undried film used as support is in a
condition of beginning to become solid when the next layer is cast thereupon. The further layers may be applied to one
or both sides of the 1st layer. If desired, the 1st layer may be formed by allowing cellulose ester soln. to run directly into
a pptg. bath. App. is described. In Brit. 461,593, Feb. 19, 1937, an acetylation soln. of cellulose triacetate, where the
catalyst has been neutralized immediately after completion of acetylation, is cast in an aq. pptg. bath contg. 7-20% AcOH
and the film or foil thereby obtained is washed and dried. Cellulose acetates contg. an Ac content of not less than 59%
calcd. as AcOH are used. The soln. is preferably subjected to stabilization before being used for film formation. This
may be effected by heating the soln. for several hrs. at above 20° after neutralization of the catalyst. The pptg. bath is
preferably kept below 30°. Slit-casting app. may be used and the film-forming soln. may contain more than 10% of
cellulose triacetate. The film may be stretched during coagulation. Softening agents, e. g., Ph3PO4, Bu3PO4, may be
added to the film-forming soln. Softening agents, e. g., glycerol, diglycerol, glucose, may be added to the washing baths.
The film may be washed with MeOH, C6H6 or other org. liquid prior to the drying by heat. App. is described.
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103. Determination of glycol or glycerol in dilute solutions containing oxidizable impurities

By Schaefer, Wm . E.
From Industrial and Engineering Chemistry, Analytical Edition (1937), 9, 449-50. Language: Unavailable, Database:
CAPLUS
The direct pyridine-Ac2O method cannot be employed directly in the analysis of a 5% glycol soln. because the water in a
2-ml. sample contg. 0.1 g. glycol would require 10.8 g. of Ac2O. By adding pyridine to the original soln. and then distg. till
the temp. reaches 110°, the greater part of the water can be removed without loss of glycol. Then the acetylation
reaction can be carried out. In calcg. the results it is necessary to assume that the reaction goes to only 97.9%.
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104. Acetylation. II. Effect of different substances on the formation of p-aminobenzoic acid in rabbits
By Harrow, Benjamin; Mazur, Abraham; Borek, Ernest; Sherwin, Carl P.
From Biochemische Zeitschrift (1937), 293, 302-4. Language: Unavailable, Database: CAPLUS
cf. C. A. 27, 5422. p-Aminobenzoic acid is partially acetylated when injected into rabbits, the process being definitely
increased by insulin injection. This observation led the authors to try the effect of various other substances which were
injected in equiv. amts. It was found that glucose, fructose, maltose, lactose, sucrose, AcOH, lactic, succinic acid,
glycerol, oleic acid, glutaminic acid and glycine caused an increase in the acetylation of p-aminobenzoic acid ranging
from 41 to 240%, glutathione and NaCl alone having no effect on this process.
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105. The effect of hydroxyl group and acetylation on the apparent diene values of soybean and vegetable oils
By Bickford, W. G.; Dollear, F. G.; Markley, K. S.
From Oil and Soap (Chicago) (1938), 15, 256-9. Language: Unavailable, Database: CAPLUS
SciFinder® Page 57
Diene values (D nos.) of 12 org. compds. and 18 oil samples are tabulated. Some of the av. D nos. by the Ellis 3-hr.
reflux toluene method and Kaufmann 20-hr. sealed-tube toluene method, resp., are anthracene 140.3, 140.2 (calcd.
142.5); acetone glycerol 19, 8.6; ethylene glycol 87.5, 57.8; glycerol 79, 53.5; Me ricinoleate 16.6, 3.1; Me
acetylricinoleate 2.8, 0.2; α,α'-distearin 0, 0; castor oil (I) 10, 3.2; acetylated I 1.0, 0.2; oiticica oil (II) 56.0, 54.5;
acetylated II 51.3, 45.0; tung oil (III) 67, 64.2; acetylated III 62.9, 56.4; extd. soybean oil A (IV) 1.7, 0.7; acetylated IV
16.3, 8.2; edible soybean (V) 0.7, 2.0; and acetylated V 1.8, 6.0. Tests on soybean oil show that the D nos. increase with
increased values for peroxides and other oxidation products. The data on this test were related within the limits of exptl.
error by the equation: D no. = 0.226 hydroxyl no. + 0.0127 peroxide no. The addn. of 5% butyraldehyde, crotonaldehyde
or octylaldehyde to refined soybean oil did not appreciably affect the D no. Conclusions: Neither method investigated
measures the true extent of conjugation in oils of low D no. Hydroxyl groups, peroxides and possible other oxidation
products influence the magnitude of the D no. Pure hydroxylated compds. having appreciable initial D nos. were found to
have little or no D no. after acetylation. However, soybean, perilla and linseed oils which have low initial D nos. have
larger D nos. after acetylation.
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106. Reciprocal action of acetylketene and alcohols. I

By Tsukervanik, I. P.; Ermolenko, I. A.
From Bull. univ. Asie centrale (1938), 22, 215-20(in German, 220). Language: Unavailable, Database: CAPLUS
The reaction between acetylketene and various alcs. and some other compds. has been investigated. The acetylation
proceeds even in the cold in the absence of catalysts. The catalysts tested were quinoline, H2SO4 and ZnCl2. Only in
acetylating glycerol the presence of H2SO4 is of advantage. The reaction proceeds smoothly and the yield is almost
theoretical in the case of primary and secondary alcs., whereas the acetylation of tertiary alcs. proceeds much more
slowly. Glycerol and glycol give a mixt. of mono- and diacetates. Unsatd. alcs. react only with the HO group with the
formation of normal acetates. The acetylation of p-anisidine gives 98% of pure acetate. Aspirin is obtained in 96% of the
theoretical yield from salicylic acid.
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107. Glycerol monolactate triacetate

By Lock, Ritchie H.
CAPLUS
Glycerol monolactate is treated with an acetylating agent such as Ac2O in a proportion at least sufficient to acetylate the
3 OH groups in the lactate. U. S. 2,107,203 relates to the use of glycerol monolactate triacetate as a plasticizer for
cellulose derivs. such as the nitrates or acetates.
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108. Glycerol ethers of cellulose. II

By Shorygin, P. P.; Rymashevskaya, Yu. A.
From Zhurnal Obshchei Khimii (1938), 8, 1903-8(in English, 1908-9). Language: Unavailable, Database: CAPLUS
cf. C. A. 32, 1925.7. In the prepn. of the glyceryl ethers the addn. of 1% (ClCH2)2CHOH (I) to pure ClCH2CHOHCH2OH
is sufficient to cause complete bridging of the linear chains in cellulose and render the ether completely water-insol.; the
addn. of 0.2% of I gives a product that is 40% water-sol. Based on viscosity detns. with aq. and cuprammoniacal solns.
of the mono- and di-glyceryl ethers the destruction of cellulose mols. during etherification may be greatly reduced by
careful operation. Acetylation of the mono-(II), di-(III) and tri-glyceryl (IV) ethers of cellulose gives incompletely esterified
products. II with Ac2O in the presence of H2SO4 yields the tetraacetate, sol. in both AcOH and Me2CO; III and IV do not
esterify completely and form acetates insol. in AcOH and Me2CO. II nitrated with H2SO4-HNO3 mixt. gives a tetranitrate,
sol. in Me2CO; III and IV form nitrates, insol. in Me2CO. Since the transverse bridges linking the primary valence chains
in water-insol. glyceryl ethers are not destroyed during acetylation or nitration the esters obtained are insol. in org.
solvents.
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109. Drastic saponification method for difficultly saponifiable esters
By Shaefer, Wm. E.; Piccard, Jean
From Industrial and Engineering Chemistry, Analytical Edition (1938), 10, 515-17. Language: Unavailable, Database:
CAPLUS, DOI:10.1021/ac50125a004
A method was desired for sapong. such terpene esters as bornyl and fenchyl phthalates and esters of abietic acid. It
was necessary to find a solvent with sufficiently high b. p. which did not discolor with strong alkali, as do most primary
alcs. other than MeOH. A reagent prepd. by dissolving Na in tert-BuOH used in glass app. in accordance with the usual
procedure proved satisfactory for sapong. bornyl phthalate. With esters of abietic acid, the butyl alc. was replaced by
cyclohexanol. The insoly. of Na cyclohexanolate was overcome by adding MeOH which was ultimately removed by
boiling. Weigh samples of suitable size into acetylation flasks and introduce a weighed portion of the solvent prepd. as
follows: Add about 9.3 g. of Na to 500 ml. of cyclohexanol, attach a reflux condenser and add 250 ml. of MeOH in small
portions. Reflux overnight, cool and preserve the reagent in a well-stoppered bottle. After adding this reagent to the
ester, attach a condenser to the flask and place in an oil bath at about 150°. Introduce a slow stream of N2 for 30 min.
During this time the MeOH is allowed to escape. Then rearrange the tubing connections and pass N2 very slowly
through the long tubing of the condenser and continue heating overnight. This causes sapon. to take place in an atm.
free of O2 and CO2. Remove the condenser, add 50 ml. of abs. EtOH which has been neutralized to phenolphthalein
and, if necessary, attach the flask to an Allihn condenser through which water is flowing and heat until the reaction mixt.
dissolves completely. Titrate with 0.1 N H2SO4 and add enough 0.1 N NaOH to make the soln. basic to phenolphthalein.
Add pieces of Si carbide, or porous plate, to prevent bumping and boil for 30 min. Cool and titrate with 0.1 N H2SO4 to a
phenolphthalein end point. If this drastic sapon. method is applied to dark colored substances it is better to use 0.5 ml. of
1% thymol blue in alc. as indicator. The method applied to a sample of com. Me abietate gave a sapon. no. which was
93.1% of the theoretical value. A Zeisel detn. gave 9.09% OMe, which indicates a purity of 92.7%. The method cannot
be used in the presence of glycerol derivs. and, presumably, of glycol derivs.
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110. Condensation of organic metal derivatives with acylated compounds

By Rozenbroek, Meindert D.
Esters of aliphatic carboxylic acids having 4 or less C atoms in the mol. are heated with alcoholates, phenolates or org.
metal compds. in which a H atom attached to C is substituted by the metal, whereby condensation occurs, the metal salt
of the lower aliphatic carboxylic acid being split off. In a modification, hydroxy fatty acids acylated at the OH group with
aliphatic, aromatic, alicyclic or heterocyclic carboxylic acids are condensed with the alcoholates, etc. The metal compds.
may contain reactive groups such as COOH, CO or SO3H or other groups contg. S or N. Among examples, (1) BuONa
is heated with acetylated octanol-2, acetylated ricinoleic acid and terpenyl acetate (I), (2) AmONa is heated with
acetylated cetyl alc., (3) Na is dissolved in BuOH and caused to react with terpineol and the resulting compd. heated with
I, (4) the ether-fatty acid obtained from acetylated castor oil fatty acid and BuONa is sapond., condensed with glycol
chlorohydrin or glycerol chlorohydrin and sulfonated to give a wetting agent and (5) the Na compd. of glycerol is heated
with acetylated wool fat and with acetylated hydroquinone. The Na soaps of the ether-fatty acids may themselves be
sulfonated and the COOH group sapond. The ether-fatty acids may also be condensed with hydroxyethanesulfonic acid
or taurine to give textile assistants.
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111. A constant-temperature bath for Stodola's acetylation microapparatus

By Cassidy, Harold G.
From Industrial and Engineering Chemistry, Analytical Edition (1938), 10, 456. Language: Unavailable, Database:
CAPLUS, DOI:10.1021/ac50124a025
The acetylation app. is partially immersed in glycerol in a well which is heated by the vapors of a suitable refluxing liquid.
The vapors are returned by a short side-arm condenser which is connected in series with and following the condenser of
Stodola's app.
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112. [Report of] chemical section

By Sen, H. K.
From Indian Lac Research Inst. Ann. Rept. (1938), 3-16. Language: Unavailable, Database: CAPLUS
SciFinder® Page 59
Av. mol. wts. of shellac fractions are: (a) by the Rast camphor method, hard resin (I) dewaxed, ether-extd. and pptd. from
alc. 1760; I dewaxed and ether-extd. 1827; I not dewaxed and extd. with ether without heat-treatment and air-dried 1588;
I dewaxed and ether-extd., dissolved in Na2CO3 and pptd. with acid 1370; bleached lac 949; shellac (not dewaxed) 1006;
soft resin 478; mixt. of 30% soft resin and 70% I, 1104; (b) by cryoscopic method in dioxane after 30 min., I dewaxed and
ether-extd. 1933; after 6 h., I 1326. K2Cr2O7 solns. of appropriate strengths in sealed tubes were more satisfactory than
I2 solns. for comparing the color of bleached solns. of lac. A new method is described for a rapid, semiquant. bleaching
test for lacs. Expts. on the keeping quality of seed lac showed that the lacs, when bleached in the presence of quinoline
or pyridine, had better life under heat and better keeping quality. Bleached lac varnish in which dioxane was used as
solvent did not suffer esterification and consequent impairment of the drying quality. The pH of a 10% cut of wax-free
shellac in 1% soda soln. was found by means of a glass electrode and vacuum-tube potentiometer to be 7.5. On diln.
the pH rose slightly, probably owing to hydrolysis of the salt, Na shellacate. On progressive bleaching with NaOCl the pH
rose to 9.15 and fell during 24 h. to 8.9. Hard lac resins prepd. from shellac by cold polymn. with urea in acetone soln.
formed water-resistant films which showed no "greening" effect on Cu, even on baking at 150° for 5-6 h., but which had
little life under heat and lacked flow. Similar resins sepd. from an acetone soln. of shellac at 5-10° possessed all the
properties of those obtained by the acetone-urea method and further possessed some flow and life (20 min at 150 ± 1°).
The soft resin from shellac, of acid value 100-5, had unfavorable properties which were improved by heating with H3PO4
with or without solvents like Me2CO or alc. The resulting modified soft resin was sol. in alc. and other solvents to give, on
air-drying or baking, a varnish of improved adhesion and flexibility. A further modification was effected by esterifying the
soft resin with HOCH2CH2OH or other polyhydric alcs. and then combining it with suitable proportions of maleic acid.
The resulting resin was sol. in benzene or other hydrocarbons and, on addn. of a little Co linoleate, gave an air-drying
varnish of good elasticity and adhesion (cf. Venugopalan, C. A. 33, 4062.8). Condensation of the soft resin with PhNH2
and HCHO gave a resin sol. in alc. + benzene which was an air-drying varnish. Shellac dissolved in PhNH2 and
condensed with paraformaldehyde in the presence of small quantities of HOAc, phthalic acid, etc., produced a
thermoplastic resin, sol. in alc. + benzene, and with higher softening and m.-p. ranges than shellac. Preliminary expts.
on the treatment of shellac with H3PO4 in presence of Me2CO or fusion of shellac under boiling H2O contg. 1-2% H3PO4
yielded products with improved properties. Shellac acids, from sapon. of shellac, on treatment with HOCH2CH2OH and
phthalic anhydride, were reduced in acidity from 154 to 79. Preliminary expts. showed that kiri, treated with gaseous NH3
for 48 h. at room temp. in a closed vessel, and then extd. with H2O at 5-10°, yielded an ext. contg. the NH4 salt of a very
soft resin of acid value 130-40, and a residue contg. an NH4 salt sparingly sol. in cold H2O, which on acidification with
HOAc yielded a hard resin. This process, extended to shellac and seed lacs, yielded 65-70% of a hard resin of acid
value 56, sapon. value 208, Wijs I value 12.81, softening and melting range 83-93°, and life at 150 ± 1° 31 min.
Acetylation of shellac below 5° showed that only the soft resin was dissolved and acetylated this indicated the
predominance of free hydroxyl groups in it. By acetylation at 20-5°, soln. of the whole mass took place, but the product
could be sepd. into ether-sol. and ether-insol. fractions. Acetylation at the boiling temp. of Ac2O gave a product wholly
ether-sol. This indicated that the pure resin of shellac (α-lac) is composed of oxygenated groupings not readily affected
by Ac2O in the cold, and hence the absence or scarcity of free hydroxyl groups. The free carboxyl group in hot
acetylated shellac was readily neutralized with glycerol or glycol in presence of the catalyst Al2(SO4)3. The resulting
ester, of acid value as low as 5, was a promising varnish material. Aleuritic acid in excess dioxane was treated with dry
HCl gas for varying lengths of time and at various temps. Results indicated that the sapon. value increased and acid
value decreased with increased time and temp. The lowering of the acid value indicated mol. enlargement through
condensation of the COOH of one mol. with the OH of another, the product being a mixt. of compds. of varying mol.
dimensions. Condensation of 8 to 10 mols. was obtained by 24-h. treatment. Heating aleuritic acid alone for 8-10 h. at
130-60° gave a product similar to that just described, but at temps. of 180-200° polymn. to a soft, rubbery product took
place. Methods for tech. prepn. of aleuritic acid are described. Dry distn. of 100 g. aleuritic acid with 40 g. CaO yielded
19 l. of gases, 20 cc. H2O and 64 cc. oil. The gas contained CH4, H, CO, N and O. The oil on vacuum distn. yielded
heavier fractions showing UV fluorescence and hence probably contg. hydrocarbons, and middle fractions yielding a
ketone giving a semicarbazone, m. 160-1°, mol. wt. 331, N 14.0% and I value 106-10. The tentative structure assigned
is (CH2)7CH: CH(CH2)7CO. Treatment of 100 g. shellac with 200 cc. Me acetone produced first a soln. of the soft resin
and then a colloidal dispersion of the hard resin and wax. Addn. of 10-15 cc. N(C2H4OH)3, vigorous shaking and
standing for 24 h. gave a soln. to which H2O up to 3-4 l. could be added without pptn. of the resin. Addn. of dil. solns. of
NaCl, AlCl3 or HCl gave poor results in pptn. of pure resin.
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113. Glycerol derivatives of cellulose

By Danilov, S. N.; Dyn'kin, M. E.; Orlova, N. I.; Rabinkov, A. A.
From Zhurnal Obshchei Khimii (1939), 9, 1674-81. Language: Unavailable, Database: CAPLUS
SciFinder® Page 60
An attempt was made to prep. water-sol. glyceryl ethers of cellulose from alkali cellulose and glycerine monochlorohydrin
(I), epichlorhydrin (II), and glycidol (III). Alkali cellulose was prepd. by the action of 33% NaOH soln. on linters contg. α-
cellulose 95.6, moisture 3.8, Cl 0.015, ash 0.25 and fats, etc., 0.15%. In attempts at etherification in pyridine, there was
no reaction at low temp., and tarring occurred at higher temp. Direct action of I on alkali cellulose was difficult, owing to
poor wetting. Monoglycerol ethers were formed when 8 mols. of I was used per mol. of C6H10O5. The resulting ethers
retained the fiber structure. The soly. of the ethers is adversely affected by small amounts of dichlorohydrin in I. Alkali
cellulose treated with 8 mols. of II in boiling acetone for 24 hrs., poured in water, neutralized with acetic acid and dried
with dry air at 50° gave ethers insol. in org. solvents, but swelling in formic acid; glycerol residue per C6H10O5 was 1.02.
Alkali cellulose heated for 24 hrs. in an acetone soln. of III, in the ratios III:C6H10O5 2:1, 4:1, 6:1, 8:1 each for 24 hrs.,
10:1 for 30 hrs. and 8:1 for 48 hrs. gave ethers contg., resp., glycerol residue per C6H10O5 0.12, 0.35, 0.61, 0.94, 1.03,
1.88 with the water solubilities 1.7, 2.9, 6.3, 8.9, 12.3 and 39.9%. Nitration and acetylation of the ethers showed those
from III contained more OH groups than those from II. The nitrated products were soluble in acetone; insol. in alc.-ether
mixts. Ethers prepd. from II contained no Cl.
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114. Esters of carboxylic acids

Sulfo carboxylic acids or polycarboxylic acids are transformed into esters by treating either the free acids, their acid salts,
their substitution products, anhydrides, halides or esters with hydroxyalkyl esters or N-hydroxyalkyl amides of resinous
acids which contain in the alkyl residue at least one free OH group, or by acetylating the hydroxyalkyl or aminoalkyl
esters of sulfo carboxylic or polycarboxylic acids which possess at least one nonesterified acid group and which contain
in the alc. residue at least one free OH or NH2 group. As sulfo carboxylic or polycarboxylic acids are used: sulfoacetic
acid, sulfosuccinic acid, phthalic, isophthalic, adipic, naphthalic, hexahydrophthalic acids. As hydroxyalkyl esters are
used the not-completely esterified esters of polyhydric aliphaticalcs., such as glycol, glycerol, mannitol and glucose, with
resinous acids, such as abietic acid, the acids of colophony, etc. The products obtained are used in textile industry as
auxiliary, deterging, wetting and softening agents. Fiber sensitive to alkali is not affected by the alkali salts of the
products.
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115. Constitution of starch, a preliminary report

By Tuzuki, Yoziro
From Nippon Kagaku Kaishi (1921-47) (1939), 60, 710-16. Language: Unavailable, Database: CAPLUS
Potato starch, vacuum dried at 100°, was heated while stirring in 6-8 times its vol. of glycerol (dehydrated by vacuum
distn.) and the product was poured into alc., pulverized and filtered under pressure. The ppt. was boiled in alc. for 2 hrs.
and vacuum dried at 80-90° and measured for the glycerol content (Zeisel and Fanto's method), which was 0.548, 1.82,
4.06 and 6.72% when the mixt. was heated for 2, 4, 6 and 8 hrs., resp., at 180°, and 14.6% when heated for 10 hrs. at
200°. Potato starch acetylated by mixing with pyridine and anhyd. AcOH at room temp., then washed in water and dried
after 24 hrs., and repptd. twice from CHCl3 and alc., was similarly glycerolized, and the glycerol content of the product
was 1.16% when heated for 6 hrs. at 170°, and 1.26, 2.56 and 5.75% when heated for 6, 8 and 15 hrs., resp., at 180°.
Thus, a longer application of a higher temp. increased the glycerol content of the glycerolized products, this suggests that
glycerol combines with one terminal radical of a long C chain forming starch. When broken up into shorter chains by
heat, more glycerol is taken up. On the basis of the glycerol content, the mol. wts. of these glycerides and acetyl
glycerides were computed and found to be fairly close to the mol. wts. estd. from the lowering of the f. p. of the aq. solns.
of the glycerides and the C2H4Br2 solns. of acetyl glycerides. Wheat starch was similarly glycerolized, and the glycerol
content of the product was 1.37, 2.36, 3.64 and 8.85% when heated for 4, 8, 16 and 32 hrs., resp., at 180°; that of the
product of the acetylated starch was 0.97, 1.58, 2.43 and 5.67% when heated for 4, 8, 16 and 32 hrs., resp., at 180°.
The decompn. of wheat starch was slightly less than that of potato starch. The mol. wts. of the glycerides and acetyl
glycerides from wheat starch tallied fairly well with those estd. from the lowering of the f. p. The viscosity of the aq. solns.
of the glycerides and of the dioxane solns. of the acetyl glycerides at 20-25° was detd., and from this Staudinger's const.,
Km, was estd. (C. A. 32, 766.4). The viscosity decreased with the further breaking up of the starch chain, and Km was 8
× 10-4 for the compds. with relatively small mol. wts. and 3 to 5 × 10-4 for those with large mol. wts. As judged from the
viscosity measurements, the structure of starch is in accord with Haworth's postulate (C. A. 25, 4529) when it is a
relatively short chain, but agrees with Staudinger's theory (loc. cit.) when it is a long chain.
~0 Citings

SciFinder® Page 61
116. [Report of] chemical section
By Sen, H. K.
From Indian Lac Research Inst. Ann. Rept. (1939), 4-22. Language: Unavailable, Database: CAPLUS
The acid value of pure lac resin was 58.4 and of the acid salt was 29.0; hence the resin is dibasic. The equiv. wt. is
therefore calcd. to be 959 and the mol. wt. 1900. Detn. of the mol. wt. by the Rast method gave values from 1900 to
2000. Similarly, soft resin is monobasic and its mol. wt. is 535 (cf. Palit and Bhattacharya, C. A. 33, 8426.7). Satn. of
shellac with gaseous NH3, and subsequent extn. with H2O at different temps. gave fractions with yields, acid and sapon.
values as follows: I at 5-10°, 2%, 133, 310; II at 10-20°, 5%, 113, 310; III at 20-5°, 5.1%, 101.4, 300; IV above 25°, 75-
80%, 56, 210. A decolorized and filtered alc. soln. of fraction I, hydrolyzed with KOH for 24 hrs. at room temp. and then
treated with CaCl2, yielded insol. Ca salts of resin acids. Decompn. of these salts with H2SO4, extn. with ether and
evapn. of the solvent, extn. of the residue with petroleum ether and evapn. yielded a crystalline acid m. 55-6°, mol. wt.
(Rast) 244-50, acid value 219, proposed formula, C14H32O3. Fraction IV appeared to be mostly hard lac resin of acid
value 56. Oxidation of aleuritic acid or shellac with strong HNO3 gave suberic acid and, in the case of shellac, a liquid
product. Stopping the oxidation with concd. HNO3 at an intermediate stage gave a liquid substance almost
corresponding to the unknown acid HOOC(CH2)5(CHOH)2(CH2)7COOH. Methylation of shellac with CH2N2 indicated
that there are aromatic or hydroaromatic hydroxyl groups in shellac. Distn. of shellac with CaO yielded distillates most of
which could be divided into terpenes and polyterpenes, and 5-7% of which contained aromatic and hydroaromatic
phenols. The sp. heat of kusum shellac at 0° is 0.53 and at 25° is 0.39. A mixt. of equal parts of soft resin, PhOH or
cresol, and HCHO with 5-10% NH3, heated at 100° for 2 hrs. and 120-30° for 2 hrs. longer, yielded a transparent, hard
and brittle product whose soln. in alc. + benzene gave a good air-drying varnish (cf. Venugopalan and Sen, C. A. 32,
9528.3). The acidity of shellac acids heated with HOCH2CH2OH at 140° for 4-5 hrs. in the presence of H2SO4 was
reduced from 154.4 to 27.69. Use of glycerol instead of HOCH2CH2OH reduced the acidity to 44.48. Properties of these
products are given. Condensation of shellac acids and shellac with phenols and HCHO yielded products whose acidities
were reduced from 184.1 to 75.5 and from 70 to 29.08, resp. Acetylation of the product from shellac acids yielded a
material of acid value 4.43, which formed a good air-drying varnish. Shellac, shellac acids, aleuritic acid, etc., may be
condensed with HCHO and urea, the purpose being to reduce the no. of free hydroxyl groups by condensation to
formals. Subsequent treatment with urea may then be carried out without introducing rapid infusibility. Heating at 120° a
mixt. of 100 parts each of shellac, HCHO and BuOH produced mixed formals. Refluxing this mixt. with 25 parts urea for
2 hrs. and removal of excess solvents and reagents leaves a resin sol. in a 1:1 mixt. of alc. + benzene or toluene, which
may be used either as a quick-baking varnish (10-15 minutes at 80-90°) or as the binding medium for the prepn. of wood-
flour-filled molding compns. (cf. Venugopalan and Sen, C. A. 33, 6071.5). Condensation of 50 g. aleuritic acid with 15 g.
phthalic anhydride at 180-90° for 20 min., heating 2 hrs. with 70 cc. 40% HCHO, soln. of the product in BuOH, addn. of
12 g. urea and refluxing for 2 hrs. yielded a product which, when dissolved in alc. + benzene or benzene + toluene, was
an adhesive. Ba aleuritate formed a very promising transparent adhesive. Improved tech. methods for production of
aleuritic acid are described.
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117. Egonol. XI. The active hydrogen atoms of egonol attached directly to carbon
By Kawai, Sin'iti; Sugiyama, Noboru; Nakamura, Takao; Komatu, Kano
SciFinder® Page 62
Egonol (I), which has only 1 HO group, gives 2 mols. CH4, and acetylegonol (II), with no free HO group, gives about 1
mol. CH4 with MeMgI. Since it has been definitely established that I is a 2-phenylcoumarone and not, as was formerly
believed, a 2-phenylchromene, the question arose as to what position the active H atom occupies in the new formula. In
2-phenylcoumarone derivs. all the double bonds form an uninterrupted conjugated system. Hence the electron densities
of the 3-, 4- and 6-C atoms of I are increased by the "+M" effect of the isolated electron pairs of the methoxy and furan O
atoms. Hence the 3-, 4-, and 6-atoms should be more or less activated. Of the various possible mesomeric states, that
represented by the formula, would seem to be the one most likely to occur (R = AcO(CH2)3; Q = 3,4-CH2O2C6H3), so that
when II is treated with Me-Mg++I- the 4-H atom, as a proton, is removed as CH4 and replaced by MgI to form an organo-
Mg compd. (III). To test this conception, MeMgI in abs. ether was added to II in anhyd. pyridine. CH4 was evolved but
the resulting III formed with the grignardized pyridine and ether an exceedingly difficultly sol. colorless complex which
with BzCl or CO2 did not give the expected 4-Bz or 4-CO2H deriv. of II. When it was attempted to get around the ether-
insoly. of the complex by driving off the ether immediately after the grignardization and replacing it by anhyd. pyridine the
complex still remained insol. and did not react with CO2. The following indirect method was then tried. Since the
coumarone nucleus tends to assume naphthalene-like arom. characteristics, the olefinic properties of the 2,3-double
bond must be weakened and it might be expected that in the bromination of II the Br, before adding at the 2,3-position,
would, through the intermediate III, replace the 4-H atom. When 1 mol. Br was added dropwise to II in AcOH it was
immediately decolorized and faint white vapors (HBr) arose from the surface of the AcOH, with formation of 4-
bromoacetylegonol (IV), m. 124.5-5°, which turned yellow with C(NO2)4, gave a neg. egonol reaction and formed a deep
orange-red soln. in concd. H2SO4. The yield was much less than 100%, however, because a mixt. of poly-Br derivs. was
formed as byproduct. In a further attempt to introduce the likewise "electrophilic" nitro group by nitrating II in Ac2O, a
lemon-yellow mononitro deriv. (V) of II, m. 160°, was obtained with the greatest ease; it was, however, not the expected
4- but probably the isomeric 3-nitro compd. It gave a pos. egonol reaction and a deep indigo-blue color (blackening in a
few sec.) with concd. H2SO4; when the oxidn. was carried out on a larger scale, the deep orange-red 3-nitronoregonolidin
acetate, m. 144-5°, was isolated. The filtrate from V yielded a small amt. of the lemon-yellow 4-isomer, m. 161 °, giving a
neg. egonol reaction and an emerald-green color (blackening in a few sec.) with H2SO4, and a still smaller amt. of the 6-
isomer, m. 139°, giving a pos. egonol reaction and a lemon-yellow color (turning brown in a few sec.) with H2SO4. With
the 4-nitro compd. the egonol reaction remained neg. even after heating 20 h. with H2O2 in AcOH. When a mixt. of IV
and KOAc was boiled with alc. there was no reaction but with boiling AmOH the Ac group was split off with formation of
4-bromoegonol, m. 164-5° and regenerating IV on acetylation; since the Br atom is not replaced by AcO, it may be
concluded that it is not on the α-C atom of the AcOCH2CH2CH2 side chain. IV was recovered practically quant. after
ozonization 10 h. in AcOEt. Cautious oxidn. with CrO3 or KMnO4 (in acetone) also produced no change. Finally, with
H2O2 and AcOH at a somewhat higher temp. (60-70°) than in the oxidn. of II, the only cryst. oxidn. product obtained was
piperonylic acid; the liq. product (mixt. of acids) gave with PhCOCH2Br a small amt. of a cryst. racemic phenacyl ester,
2,5,3,6-Br(MeO) (AcOCH2CH2CHOH) (3,4-CH2O2C6H3CO2)C6HCO2CH2COPh (VI), m. 172-3°, which on sapon. with
KOH-MeOH yielded PhCOCH2OH, piperonylic acid and a liq. phenolcarboxylic acid contg. Br and giving a dark-blue
FeCl3 reaction. The structure (ED 0.59) given in part II (C. A. 33, 601.4) for the Me styraxate obtained by oxidizing I with
H2O2 at 80° and methylating the product with CH2N2 must now be replaced by the isomeric structure 2,3,5-
(MeO)2[HOCH2CH(OH)CH(OH)]C6H2CO2Me (VII) (ED 0.55); the faint green FeCl3 reaction which had been obsd. must
have been due to an incompletely methylated phenolic impurity. ED for BzOMe is 0.45, and a substance having the
formula first proposed, which contains no conjugated double bond, should not show such a high specific exaltation.
Oxidn. of derivs. of I with H2O2-AcOH at 50-5° does not attack the HOCH2CH2CH2 side chain (C. A. 33, 3788.2); at 60-
70°, 1 HO group is introduced (see VI, above), and at 80° the side chain is oxidized to glycerol (VII). The Zerevitinov
micromethod of detg. active H gave for II, which would be expected to contain 1 active H atom, somewhat low values
(0.55-0.62); 3 compds. which were not expected to contain active H gave the following values: IV, 0.06-0.24; 3,4,6-
tribromoacetylegonol, 0.31-0.35; 6-methoxy-2-phenylcoumarone, 0-0.02. The 7-MeO group of I and its derivs. therefore
has a great influence on the activation of the 4-H atom. The structures previously assigned (C. A. 33, 1324.4) to the
bisegononyl selenides obtained from II and SeO2 must now also be discarded. The α-compd., which does not give the
egonol reaction, must be the 4,4'-isomer, and the β-compd., which gives a pos. egonol reaction, must be the 3,3'-, 3,4'-,
3,6'-, 4,6'- or 6,6'-isomer.
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118. Diketene-a new industrial chemical

By Boese, A. B., Jr.
DOI:10.1021/ie50361a004
SciFinder® Page 63
Of the 4 structures proposed for diketene, that of vinylaceto-β-lactone H2C: C.CH2.CO.O (I) appears to account for the
reactions of diketene most satisfactorily with but 1 exception, the formation of pyruvaldehyde on ozonolysis. The primary
importance of I is based upon its exceptional chem. reactivity and consequently in the products which may be
synthesized from it. Its most common reaction is the addn. of substances with an active H atom to yield compds. contg.
the AcCH2C:O group. Thus, I reacts with H2O in the presence of catalysts to give AcCH2CO2H which in turn decomp. to
Me2CO and CO2. With alcs. in the presence of acid catalysts, esters of AcCH2CO2H result. This method of synthesizing
esters is superior to the classical Na condensation of AcOEt both academically and industrially. This reaction is a
general type applicable to all aliphatic alcs., primary to tertiary, alc. ethers, chlorohydrins, substituted alcs., glycols,
glycerol and phenols. I and primary aromatic mono- and polyamines react smoothly to yield the corresponding
acetoacetylamines in a high degree of purity and with excellent yields. Similarly I also reacts with aq. solns. of NH3,
primary and secondary aliphatic amines. Thus, compds. such as AcCH2CONHPh, Ac-CH2CONH2, and similar type
substances can be readily prepd. With urea or disubstituted ureas, I reacts in an inert solvent, yielding 4-methyluracil or
its homologs. PhNHNH2 and I at room temp. yield the phenylhydrazone of AcCH2CONHNHPh. At higher temps. 1-
phenyl-3-methyl-5-pyrazolone is obtained in excellent yield. With aromatic hydrocarbons in the presence of AlCl3 I gives
rise to 1,3-diketones such as BzCH2Ac. Halogens add to I to form γ-haloacetoacetyl halides and β-butyrolactone is
formed when I is hydrogenated. I may be further polymerized by catalysts to yield a tetramer of ketene, dehydroacetic
acid, which is also a very valuable reagent because of the large no. of com. derivs. which can be prepd. from it.
Pyrolysis of I at 500-600° converts it to ketene which is a powerful acetylating agent. B. presents an excellent summary
of the applicability of I, now available in com. quantities, in synthetic org. chemistry. 50 references are cited.
~16 Citings
119. Glycerolysis of starch and the molecular weight and the viscosity of the products
By Tuzuki, Yoziro
From Bulletin of the Chemical Society of Japan (1941), 16, 161-70. Language: Unavailable, Database: CAPLUS
On heating 8 g. of dried starch in 60 g. C3H5(OH)3 at 180° potato starch (I) gives a clear soln. in 4 hrs., wheat starch (II)
in 16 hrs., whereas rice starch (III) is insol. [α]D 30 for I falls from 165.7° to 145.5° on heating 16 hrs. and ηsp from 0.430
to 0.298; the corresponding figures for II are 178.2° to 142.0° and 1.131 to 0.506; for III 162.5° to 124.6° and 0.819 to
0.498; for the acetates of I 163° to 103.3° (in CHCl3). After heating 32 hrs. at 180° the C3H5(OH)3 content of I was
14.6%, of II 7.52%; of the acetylated products 7.47% and 5.67%; the values increase with the rise in the temp. of heating
as well as with the time of such heating. The mol. wts. of the various products were detd. from the C3H5(OH)3 content,
by the cryoscopic method in H2O and by the viscosity method. The agreement of these values shows that a glyceryl
group probably stands at 1 end of the mol. chain of the disaggregated starch. The viscosity measurements indicate that
Km of the Staudinger equation decreases with increasing mol. wt.; an equation ηsp/C = KmM + k expresses the
relationship between viscosity-concn. and mol. wt.; the values for the consts. Km and k are: glyceryl I 7 × 10-4 and 0.2;
glyceryl II 4 × 10-4 and 0.2; for the acetylated deriv. 7 × 10-4, 0.4; 5 × 10-4, 0.5.
~1 Citing
120. Dehydrated castor oil. A review. II

By Morgan, J. D.
From Paint Manufacture (1941), 11, 166-70. Language: Unavailable, Database: CAPLUS
cf. C. A. 35, 7217.3. A discussion of the manuf. of dehydrated castor oil, methods used, the bodying of the oil and its
application. Three methods of dehydration are: (1) catalytic dehydration of castor oil fat acids and esterification of these
with glycerol; (2) direct dehydration of castor oil with catalysts; and acetylation of castor oil and subsequent removal of
AcOH to leave a dehydrated oil.
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121. Configurative association of several 20-position epimeric 17(α)-hydroxypregnane derivatives with glycerol
side chains
By Reich, H.; Montigel, C.; Reichstein, T.
SciFinder® Page 64
Hydroxylation of 17-vinyl-3(β),17(α)-androstanediol (C. A. 33, 3808.2) gave the 20-position isomeric allopregnanetetrols,
characterized as the triacetates (Ia and Ib). Similarly, from 17-vinyl-5-androstene-3(β),17(α)-diol and 17-vinyl-17(α)-
testosterone, similar compds. of type II and V (C. A. 32, 7475.5) were prepd. but only in 1 isomeric form. All 4 possible
compds. IIa, IIb, Va and Vb have been prepd. and by direct rearrangement have been related to Ia and Ib. A mixt. of 2.4
g. of 17-vinyl-5-androstene-3(β),7(α)-diol 3-acetate, m. 163-5° (all m. ps. cor.) (C. A. 32, 4995.9) in 120 cc. abs. ether
with 2 g. OsO4 in 40 cc. abs. ether was kept at room temp. for 48 hrs., evapd. down, treated with 14 g. Na2SO3 in 100 cc.
H2O and 50 cc. alc. and refluxed for 4 hrs. The reaction mixt. was filtered hot and the residue was extd. with 150 cc. of
boiling 50, 60, 70, 80, 90 and 100% alc. until free from org. material. The united filtrates were concd. to 100 cc. and
shaken out with 3 l. of freshly distd. ether. The washed and dried ether ext. was evapd. down and yielded 2.4 g. of
colorless, cryst. crude product, m. 210-22°, acetylated to give 2.6 g. of light yellow resinous material. Recrystn. from
ether-pentane produced about 200 mg. of 5-pregnene-3(β),17(α),20(α),21-tetrol 3,20,21-triacetate (IIa), m. 166-8°, [α]D
19 -90.8 ± 4° (c 1.233 in acetone). Chromatographic analysis of the mother liquors over a 50-g. Al O column yielded
2 3
400 mg. IIa and 720 mg. of fine, felted needles of 5-pregnene-3(β),17(α),20(β),21-tetrol 3,20,21-triacetate (IIb),
C27H40O7, m. 123-5°, [α]D 19 -44.2 ± 3° (c 1.381 in acetone). Catalytic reduction of IIa in pure AcOH in the presence of
PtO2 gave Ia, m. 119-21°, and similarly IIb was reduced to the known Ib, m. 146-8°. A mixt. of 300 mg. IIa in 12 cc. of
2% KOH in MeOH was refluxed for 15 min., neutralized with CO2, treated with H2O and freed from MeOH in vacuo,
yielding 220 mg. of tetrol which was taken up in 80 cc. of dry acetone and shaken with 1 g. anhyd. CuSO4 for 48 hrs.
The mixt. was filtered and the filtrate was shaken with 0.2 g. of finely powd. KOH for 30 min. After filtration, the clear
filtrate was evapd. down, the residue was taken up in abs. benzene and chromatographed over 2 g. Al2O3. Elution with
100 cc. abs. ether gave 200 mg. of 20,21-acetone-5-pregnene-3(β),17(α),20(α),21-tetrol (IIIa), C24H38O4, m. 124-130°
(solidifying and again m. 156-8°), [α]D 13.5 -62.7 ± 2° (c 1.499 in acetone). The corresponding 20,21-acetone-5-
pregnene-3(β),17(α),20(β),21-tetrol (IIIb), m. 148-61°, [α]D 15 -59.0 ± 2° (c 1.101 in acetone), was similarly prepd.
Dehydrogenation of 200 mg. IIIa by refluxing for 24 hrs. with 0.5 g. (tert-BuO)3Al in 6 cc. dry acetone and 16 cc. abs.
benzene, purification over Al2O3, elution with benzene, benzene-ether (20:1), and recrystn. from ether-pentane and
acetone-pentane gave 110 mg. of 20,21-acetone-4-pregnene-17(α),20(α),21-triol-3-one (IVa), C24H36O4, m. 220-1.5°,
[α]D 15 66.7 ± 2° (c 1.244 in acetone). A similar Oppenauer oxidation of IIIb gave the corresponding 20,21-acetone-4-
pregnene-17(α),20(β),21-triol-3-one (IVb), m. 173-5°, [α]D 17 39.3 ± 2° (c 1.196 in acetone). A mixt. of 110 mg. IVa in 5
cc. AcOH and 2.5 cc. H2O was warmed at 70° for 1 hr. and, after the addn. of 2.5 cc. H2O, for a 2nd hr., the soln. was
evapd. down and the residue recrystd. from MeOH-ether, yielding 80 mg. of colorless leaflets, m. 233-5°. Acetylation
and chromatographic purification gave 74 mg. of 4-pregnene-17(α),20(α),21-triol-3-one 20,21-diacetate (Va), C25H36O6,
m. 165-6°, [α]D 15 21.6 ± 3° (c 1.251 in acetone). The corresponding 4-pregnene-17(α),20(β),21-triol-3-one 20,21-
diacetate (Vb), m. 180-1°, [α]D 15 50.2 ± 2° (c 1.416 in acetone), was similarly prepd. and proved to be identical with the
compd. of Serini and Logemann (C. A. 32, 7475.5). Tabulation of the mol. and sp. rotations of the 10 compds. shows
that the acetates of the members of the 20(β)-series have a strong pos. rotation.
~0 Citings
122. Loco weeds. V. Further studies on the constituents of Astragalus earlei

By Stempel, Arthur; Elderfield, Robert C.
From Journal of Organic Chemistry (1942), 7, 432-43. Language: Unavailable, Database: CAPLUS,
DOI:10.1021/jo01199a007
SciFinder® Page 65
cf. C. A. 36, 6158.7. When β-earleine (I) isolated from the loco weed Astragalus earlei (cf. Pease and E., C. A., 34,
32781) is thermally decompd. NMe3, identified as picrate, m. 228-9°, and AcH, identified as the 2,4-
dinitrophenylhydrazone, m. 164°, are formed. From this it seems that I is identical with choline. This is supported by the
prepn. of the picrate of I, m. 247°, the chloroplatinate, m. 234-6° (decompn.), and of the acetate picrate, m. 111.5-12.5°.
It is further found that α-earleine (II) is identical with betaine, as the picrate of II m. 184°, styphnate m. 186-8° (decompn.)
and HBr salt m. 225°. The extreme soly. of the toxic principle of loco weed in H2O and EtOH suggests that it is strongly
polar and probably highly hydroxylated and that it is partially held back in the phosphotungstic acid ppt. by adsorption. In
order to obtain a better sepn., the filtrate (A) of the ppt., after being freed of phosphotungstic acid with BaOH, is evapd. to
dryness and the residue acetylated with AcO2 and pyridine. After decompn. with ice, the mixt. is extd. with CHCl3. The
ext. is washed with HCl and NaHCO3, the dried CHCl3 soln. evapd., and the residue sepd. at 5 × 10-3 mm. into 3
fractions, (B) b. up to 100°, (C) b. 100-20° and (D) b. 130-50°. Redistn. of B gives glycerol triacetate, b0.15 85-9°, which
on sapon. gives glycerol identified as the tri-Bz deriv., m. 72-3°. Fraction C on redistn. gives a product (III), b0.2 124-30°,
m. 86-7°, [α]D 25 -7.09° (c 2.822, CHCl3), 25.2° (c 2.124, EtOH). From the sapon. no. and elementary analysis, III is
found to be a diacetoxyvalerolactone. Sapon. of III according to Elek and Harte (C. A. 30, 5532.7) gives the lactone (IV),
m. 52-3°, [α]D 25 -64.7° (c 0.580, H2O); phenylhydrazide of the corresponding OH acid by heating IV with PhNHNH2, m.
114-15°, [α]D 25 42° ± 2° (c 0.558, MeOH), 45° (c 0.462, H2O). The possible structure of IV is discussed and for
comparison, d-xylomethylonic acid phenylhydrazide, m. 132-3°, [α]D 25 33° (c 0.640, MeOH), 21° (c 0.398, H2O), is
prepd. from d-xylomethylonic acid which in turn is obtained by oxidation of d-xylomethylose with Br-H2O. Oxidation of IV
with (AcO)4Pb in AcOH and comparison of the consumption of the Pb salt with that obtained by Hockett and McClenahan
(C. A. 33, 6803.4) with β-Me-d-xylopyranoside and α- and β-Me-d-glucopyranoside indicate that the OH groups in IV are
in the trans position to each other. No definite conclusion as to its structure can be drawn. Fraction D on redistn. b0.01
137-45°, m. 97-8°, [α]D 25 7.0° (c 1.920, EtOH), and is identical with acetylpinitol. The residue of the aq. soln. after extn.
with CHCl3 is highly toxic to cats. It gives a pos. Molisch test, a red-blue ninhydrin test and does not reduce Fehling soln.
On destructive distn. the vapors give a strong red pine-splinter test for pyrrole. When it was found that at least 11% of
the total N in the weed is nonbasic, the filtrate A was treated with a soln. of Reinecke salt and the ppt. formed was
decompd. with pyridine, giving a filtrate which was evapd. to dryness. The residue after repeated crystn. from MeOH and
EtOH gave white plates contg. N and S which decomposed at about 320°. The compd. is optically inactive, very sol. in
H2O, gives neg. nitroprusside and ninhydrin tests and contains no amino N. It can also be pptd. by NH4 rhodanilate. On
thermal decompn. a strong odor of amine appears and the vapors give a strong pyrrole test. The isolation of the toxic
component of the weed is rendered difficult by the presence of large amts. of carbohydrates. The glucosides are
hydrolyzed by the action of takadiastase and emulsin without affecting the toxicity. The reducing sugars and part of the
glucosides are also removed by the method of Rabaté (C. A. 31, 4058.1), using MgO, but this does not facilitate the
isolation of the nitrogenous components.
~0 Citings
123. α,γ-Benzylideneglycerols
By Verkade, P. E.; van Roon, J. D.
From Recueil des Travaux Chimiques des Pays-Bas et de la Belgique (1942), 61, 831-41. Language: Unavailable,
Database: CAPLUS
C3H5(OH)3 and 1.2 mols. BzH, heated at 145-50° for 1.5 hr. and at 165-70° for 2 hr., with passage of CO2 to remove the
H2O formed in condensation, give a liquid product (I), b4 140-50°; seeding and introduction of HCl gas at 0° give 60% of
α,γ-benzylideneglycerol (II), m. 82.5-3.5°. Acetylation of I with Ac2O and C5H5N and cooling the liquid Ac deriv. to -10°
give an Ac deriv., m. 115-16°, hydrolysis of which (short heating with 0.02 N MeONa) gives 92% of an isomer (III) of II, m.
63.5-4.5° (over-all yield of III, 6%). Under certain conditions I yields 65% of a 1:1 mol. compd. (IV) of II and III, m. 65-6°;
this also results by crystn. of equiv. amts. of II and III from petr. ether-C6H6 or H2O or by melting the components.
Whether II or IV results on the treatment of I with mineral acids apparently depends upon the cryst. nucleus present. II
and BzCl in C5H5N yield 99% of the Bz deriv. (V), m. 103-3.5°; hydrolysis with 0.02 N MeONa regenerates II. III yields a
Bz deriv., m. 103-4.5° (mixed m. p. with V, 80-2°, clears at 93°); catalytic reduction gives β-benzoylglycerol, m. 72-3°. II
gives 97% of the β-Ac deriv., m. 101-2°. The phenylurethan (VI) of II m. 190-1°; the VI from III m. 178-9°; the VI from IV
m. 157-68° and could be sepd. into its components by crystn. from C6H6. II is assumed to be the trans, III the cis form.
~3 Citings
124. Sulfanilamide acetylation as influenced by various chemicals and by vitamin deficiencies

By Martin, Gustav J.; Rennebaum, E. H.
SciFinder® Page 66
Simultaneous administration of sodium acetate with sulfanilamide reduced the degree of acetylation in the rat by 39%.
Pure glucurone did not inhibit the acetylation of sulfanilamide to the extent that the crude calcium glucuronate did.
Sodium pyruvate increased greatly the acetylation of sulfanilamide, the av. value of such increase being in excess of
300%. Alanine, dihydroxyacetone, sodium oxalacetate, calcium glycerophosphate, sodium l-malate, glycerol, dl-
galacturonic acid and glycolic acid were all neg. On the other hand, glycine, sodium succinate, sodium acetoacetate,
ascorbic acid and cysteine facilitated acetylation to a slight degree. Dextrose definitely increased acetylation. Under the
exptl. conditions of the authors neither adrenaline nor insulin increased acetylation. Acetylation of sulfanilamide was
defective in rats with a thiamine or a riboflavin deficiency.
~0 Citings
125. Steroids. XXXIV. Desoxycorticosterone saccharides. 2

By Miescher, K.; Meystre, Ch.
cf. C. A. 36, 4513.2. The extremely low soly. of desoxycorticosterone (I) in H2O can be raised 10-fold to 0.12% at 18° by
conversion into the β-d-glucoside, m. 190-5°, [α]D 109° in MeOH, which is readily sol. in aq. solns. of mono- or polyalcs.
The prepn. of other possibly more H2O-sol. saccharides was undertaken. I (10 g.) in 25 cc. alc.-free CHCl3 mixed with
20 g. of freshly prepd. dry AgCO3 was treated dropwise at 40-5° with 20 g. acetobromo-d-galactose (C. A. 23, 3904) in
25 cc. CHCl3 in 1 hr. and the mixt. was stirred for 8 more hrs. The reaction mixt. was filtered and the residue from the
evapd. filtrate was taken up in ether. Evapn. gave 21 g. of crude tetraacetate which was dissolved in MeOH and treated
with 14 g. K2CO3 in H2O for 20 hrs. at 20°. The MeOH was removed and the aq. suspension was shaken out with ether
to remove unaltered I (about 2.9 g.). Extn. with CHCl3 gave 10 g. of crude material, further purified by treating an aq.
soln. with charcoal. Recrystn. of the purified product from abs. alc. produced desoxycorticosterone β-d-galactoside,
C27H40O8, m. 195-8°, [α]20 D 136 ± 4° (c 0.965 in acetone), soly. in H2O at 18°, 0.22%, more sol. on heating. Similarly
from 10 g. I and 14 g. acetobromolactose (C. A. 19, 2476) was prepd. desoxycorticosterone β-d-lactoside monohydrate,
C33H50O13.H2O, m. 202-8°, [α]20 D 80 ± 4° (c 1.020 in MeOH), soly. in H2O, 0.34%, more sol. on heating; hepta-Ac deriv.,
m. 194-5°, [α]20 D 52 ± 4° (c 0.97 in acetone), obtained by acetylating the lactoside with Ac2O in pyridine for 2 days at
20°. Condensation of 5 g. I with 13 g. acetobromomaltose (C. A. 23, 3444) in the presence of AgCO3, followed by
reacetylation, chromatographic analysis and crystn. from acetone-ether yielded desoxycorticosterone β-maltoside
heptaacetate, m. 183-5°. A mixt. of 14 g. of 1,2,3,4-tetraacetylglucose, m. 128-9°, 14 g. acetobromolactose (C. A. 19,
2476), and 20 g. anhyd. CaCl2 was shaken in abs. CHCl3 for 3 hrs. at 20°. The mixt. was then treated with 12 g. AgCO3
and 3 g. iodine and shaken for 24 hrs. Working up gave 42% of pure 6-(β-lactosido)-d-glucose hendecaacetate,
C40H54O27, m. 192-4°, converted by treatment in CHCl3 with 15 cc. of satd. HBr in AcOH at 0° for 1.5 hrs. into the
corresponding 6-(β-heptaacetyllactosido)acetobromo-d-glucose (II), C38H51BrO25, m. 138-42°. A mixt. of 800 mg. II, 400
mg. I and 3.5 g. AgCO3 in 20 cc. CHCl3 was shaken for 15 hrs. at 40-5°. The residual product was acetylated with 7 cc.
Ac2O in 10 cc. pyridine for 24 hrs. and the product was chromatographed to remove unaltered I Ac deriv. The
amorphous impure hendecaacetate, C59H80O28, m. 120-30°, was sapond. at -15° with 0.3 N Ba(OMe)2 in MeOH for 15
hrs. Recrystn. of the product from hot alc. yielded amorphous, vitreous desoxycorticosterone 6-(β-lactosido)-β-d-
glucoside dihydrate, C39H60O18.2H2O, m. 160° (decompn. 190°), the 1st synthetic trisaccharide of a natural product.
Brief procedures are given for the prepn. of stable sterile 1% solns. of desoxycorticosterone β-d-glucoside in 10% aq. d-
glucose and of 2% solns. in 10% glycerol.
~1 Citing
126. Determination of glycerol by the pyridine acetylation method

By Moore, J. C.; Blank, E. W.
From Oil and Soap (Chicago) (1943), 20, 178. Language: Unavailable, Database: CAPLUS, DOI:10.1007/BF02593123
The removal of water from dil. glycerol solns. permits the checking of the dichromate method on dil. solns. by acetylation.
The pyridine-acetylation method checks the dichromate oxidation method very closely. The factor representing the
extent to which acetylation takes place when detg. glycerol by the pyridine-acetylation method should be 0.993.
~0 Citings
127. Constituents of the adrenal cortex and related substances. LXIV. Linking up configuration of several 17β-
hydroxypregnane derivatives with glycerol groups in the side chains
By Koechlin, B.; Reichstein, T.
SciFinder® Page 67
The hydroxylation of 17-allopregnene-3β,21-diol diacetate (I) with OsO4 by Serini (C. A. 33, 3808.2) gave only
allopregnane-3β,17β,2β,21-tetrol (III) of the 4 possible stereoisomeric tetrols although the catalytic reduction of
substance P (C. A. 33, 1388.4) gave an isomeric 20α-tetrol (IV). Similar hydroxylation with OsO4 of 4,17-pregnadien-21-
ol-3-one acetate (XI) gave a 4-pregnene-17β,20,21-triol-3-one (XII) (C. A. 33, 6869.5; 33, 6927.5) as the only isomer.
Prins (Diss. Basel. 36(1942)) also reported the formation of 5-pregnenetetrol (VII) as the only compd. formed by the
hydroxylation of 5,17-pregnadiene-3β,21-diol diacetate (VIII). The configuration of VII as 5-pregnene-3β,17β,20β,21-
tetrol was established when the reduction of its triacetate (VI) gave an acetate (V) identical with the compd. obtained by
the acetylation of III. The triol XII has been unequivocally linked configuratively with VII and III by conversion of VII to XII
by a procedure previously used in transformations in the 17α-OH series.(C. A. 36, 2561.8). To this end VII was
converted into an acetone compd. (X) by shaking with acetone and CuSO4; X was then oxidized according to Oppenauer
to the triol (IX) which was then cleaved to give XII, fully identical with the compd. prepd. by Ruzicka and Müller (C. A. 33,
6869.5) from 4,17-pregnadien-21-ol-3-one acetate (XI). A mixt. of 500 mg. VIII, m. 135-6° (all m. ps. cor.), and 555 mg.
OsO4 in 30 cc. abs. ether was kept under anhyd. conditions for 64 hrs. at room temp. and freed from ether in vacuo. The
residue was refluxed for 5 hrs. with 6 g. cryst. Na2SO3 in 60 cc. H2O and 30 cc. alc. and filtered. The black OsO4 residue
was washed with 80-cc. lots of 40, 50, 60, 70 and 90% alc. and then extd. 3 times with boiling alc. The combined filtrates
were concd. to 50 cc. in vacuo and shaken out 3 times with a total of 2.5 l. ether and afterwards with CHCl3, yielding 740
mg. and 30 mg. of crude product. The 770 mg. of crude tetrol was acetylated for 20 hrs. at room temp. with 3 cc. Ac2O in
5 cc. abs. pyridine. The mixt. was heated at 60° for 1 hr. and the crude product was crystd. from acetone-ether, giving
600 mg. of 5-pregnene-3β,17β,20β,21-tetrol 3,20,21-triacetate (VI), C27H40O7, m. 189-90° (in needles after heating at
184-5°), [α]13 D 5.9 ± 1.5° (c 0.716 in acetone). The mother liquors also gave 50 mg. VI after chromatographic sepn.
over 2.5 g. Al2O3. Hydrolysis of 262 mg. VI with 35 cc. of 2% KOH in MeOH for 15 min., concn. and diln. with 15 cc.
H2O, and neutralization with CO2 produced 190 mg. VII, m. 220-3°, [α]14 D -56.2 ± 5° (c 0.423 in acetone). A mixt. of 190
mg. VII with 2 g. anhyd. CuSO4 and 100 cc. anhyd. acetone in a well-closed flask was shaken mechanically for 44 hrs.,
filtered and shaken with dry K2CO3. After filtration and evapn. to dryness, the product was extd. with ether and crystd.
from ether-petr. ether, yielding 195 mg. (92%) of 5-pregnene-3β,17β,20β,21-tetrol 20,21-acetone compd. (X), C24H38O4,
m. 201-3°, [α]22 D -62.7 ± 2° (c 0.956 in acetone). A mixt. of 200 mg. X with 8 cc. acetone, 21 cc. abs. benzene and 500
mg. (tert-BuO)3Al was refluxed for 24 hrs. and evapd. to dryness. The residue was taken up in 100 cc. ether and shaken
vigorously with 50 cc. satd. KNaC4H4O6 soln. The ether layer was shaken out with 30 cc. KNaC4H4O6, with 2 lots of 15
cc. Na2CO3 and 2 lots of 10 cc. H2O and the aq. layer was twice extd. with ether. Evapn. of the washed and dried ether
exts. gave 240 mg. of cryst. crude product purified by chromatographic analysis over 6 g. Al2O3, Elution with benzene-
petr. ether (3:1) yielded 90 mg. of 4-pregnene-17β,20β,21-triol-3-one 20,21-acetone compd. (IX), C29H36O4, m. 146-7°
(together with a rare modification, m. 200-4°), [α]22 D 74.7 ± 2° (c 1.566 in acetone), absorption max. at 241 mµ and log ε
4.10. By warming at 70° for 2 hrs. with 2.5 cc. H2O, IX (85 mg.) was converted into the corresponding triol (XII), m. 190-
4°, identical with the 4-pregnene-17β,20β,21-triol-3-one previously prepd. by Ruzicka, as shown by the prepn. of the
diacetate, m. 196-7°, [α]18 D 135.9 ± 2° (c 1.266 in acetone).
~0 Citings
128. Acetylation in the presence of phosphoric acid

By Ciusa, R.; Sollazzo, G.
From Annali di Chimica Applicata (1943), 33, 72-3. Language: Unavailable, Database: CAPLUS
Expts. on the acetylation of alcs., phenols, polyphenols and amines with H3PO4 as catalyst are described. The calcd.
proportion of Ac2O is added to the compd., and then 7-8% of concd. H3PO4 is added gradually. In some cases the
reactions are violent. The following compds. were thus acetylated: MeOH to MeOAc; EtOH to EtOAc; glycerol to
triacetin; mannitol to its hexaacetate; glucose to β-pentaacetylglucose; lactose to a heptaacetate; starch to a triacetate;
cellulose to acetylcellulose; geraniol to acetylgeraniol; phenol to PhOAc; ο-HOC6H4CO2H to acetylsalicylic acid;
pyrocatechol, resorcinol, hydroquinone and 1,5-C10H6(OH)2 to the diacetyl derivs.; 2-naphthol to acetyl-2-naphthol;
menthol to acetylmenthol; tannin to acetyltannin; BzH to a diacetate, m. 42-3°; quinone to 1,2,4,5-tetrahydroxybenzene
tetraacetate; PhNH2 to PhNHAc; 1- and 2-C10H7NH2 to acetylnaphthylamines; triethanolamine to the tri-Ac deriv., b8 177-
9°.
~0 Citings
129. Acetolysis of trimethylene-D-mannitol. 2,5-Methylene-D-mannitol

By Ness, A. T.; Hann, Raymond M.; Hudson, C. S.
DOI:10.1021/ja01251a059
SciFinder® Page 68
2,5-Dibenzoyl-1,3,4,6-dimethylenedulcitol and the acid acetylating mixt. (I) (H2SO4, Ac2O and AcOH), shaken for 30 min.,
give a quant. yield of 2,5-dibenzoyl-1,6-diacetyl-3,4-di(acetoxymethyl)dulcitol (II), m. 87-8°. Reaction of II with 0.2 N
MeONa at room temp. for 18 hrs. gives a quant. yield of dulcitol. 2,5-Diacetyl-1,3,4,6-dimethylenedulcitol and I give 76%
of 1,2,5,6-tetraacetyl-3,4-di(acetoxymethyl)dulcitol (IIA), m. 93-4°. Evidence is presented for the assignment of the
structure of 1,3,2,5,4,6-trimethylene-D-mannitol (III) to the product of Schulz and Tollens (Ann. 289, 21(1896)). A study
of the prepn. of III shows that a 94% yield may be obtained from a mixt. of D-mannitol, 20 cc. 37% HCHO and 20 cc.
concd. HCl. III and I give 81% of 1,6-diacetyl-3,4-di(acetoxymethyl)-2,5-methylene-D-mannitol (IV), m. 129°, [α]20 D
57.6° (CHCl3, c 1.1). IV and 0.2 N MeONa at 0° for 1 hr. and at 5° for 18 hrs. give a quant. yield of 2,5-methylene-D-
mannitol (V), m. 173-4° (cor.), [α]20 D -51.4° (H2O, c 1.2); Ac2O in C5H5N gives 57% of the 1,3,4,6-tetra-Ac deriv., m.
117-18°, [α]20 D -1.3° (CHCl3, c 1.2); BzCl gives 85% of the 1,3,4,6-tetra-Bz deriv., m. 107-9°, [α]20 D -7.5° (CHCl3, c 1.6);
1,3,4,6-tetratosyl deriv., m. 177-8° (cor.), [α]20 D 3.5° (CHCl3, c 1.1), 30%. V consumes 0.99 and 1.07 mol. equivs. of
Pb(OAc)4 in 19 and 70 hrs.; 1.1, 1.14 and 1.1 mol. equivs. of Na periodate are consumed in 20 and 40 min. and 19 hrs.,
resp.; HCHO or HCO2H is not produced. The absence of HCHO proves that the glycol grouping is formed from 2 sec-
HO groups and the absence of HCO2H shows that the C atoms adjacent to the glycol grouping are concerned in the
acetal linkage. Oxidation of V with HIO4 gives methylenebis-(2-D-glycerose) (VA) which could not be crystd. but is
reduced to methylenebis(2-glycerol) (VI), m. 85-6°, optically inactive. Hydrolysis of VI with 2 N H2SO4 gives C3H5(OH)3,
identified as the tri-Bz deriv. VII and BzCl in C5H5N give a quant. yield of the tetra-Bz deriv., m. 69-71°. V (5 g.) in 50 cc.
C5H5N at 0°, treated dropwise with 6 cc. BzCl, gives 85% of the 1,6-di-Bz deriv. (VII), m. 119-20°, [α]20 D -70.3° (CHCl3, c
1.1). VII consumes 1 mol. equiv. of Pb(OAc)4 in 30 hrs. and 1.44 mol. equivs. in 72 hrs.; after 1 month 4.92 equivs. were
consumed. Oxidation of VII with Pb(OAc)4 in AcOH for 30 hrs. at room temp. gives 60% of the formaldehyde acetal of 3-
benzoyl-D-glyceraldehyde, isolated as the disemicarbazone, m. 193-5° (cor.), [α]20 D 83.6° (AcOH, c 0.9). VII, BzH and
ZnCl2, shaken for 30 min., give 83% of 1,6-dibenzoyl-2,5-methylene-3,4-benzylidene-D-mannitol (VIII), m. 151-2°, [α]20 D
61.2° (CHCl3, c 1.1). 1,6-Dibenzoyl-3,4-dibenzylidene-D-mannitol (1 g.), 1 g. (HCHO)3, 5 g. drierite and 50 cc. C6H6,
heated at 150° for 8 hrs., give 20% of VIII. The soln. of VA, obtained by oxidation of 10 g. V with 100 cc. 0.675 N HIO4 in
50 cc. H2O for 20 hrs. at room temp. ([α] 10°), when treated with an excess of hot satd. Ba(OH)2, neutralized with dil.
H2SO4, cooled to 0°, filtered, and the filtrate ([α] -14°) concd. to a sirup (8.5 g.) and catalytically reduced with Raney Ni at
100° and 133 atm., give 37% of 4-(hydroxymethyl)-5-hydroxy-6-di(hydroxymethyl)-1,3-dioxane (IX), m. 139-40°, [α]20 D
39.7° (H2O, c 1.1); IX also results in 40% yield by the action of 10 cc. N NaOH upon 1.49 g. V in 75 cc. H2O for 150 min.,
neutralization with H2SO4 and catalytic reduction. With Ac2O in C5H5N IX yields 89% of 4-acetoxymethyl-5-acetoxy-6-
di(acetoxymethyl)-1,3-dioxane, m. 93-4°, [α]20 D 12.4° (CHCl3, c 1). The isolation of V indicates that, under the
conditions of acetolysis employed, the methylene hemiacetal linkages that are formed through primary HO groups are
more easily ruptured than those formed through sec-HO groups and suggests the tentative structures for II, IIA and IV.
~4 Citings
130. Some derivatives of dialkoxyphthalides

By Manske, Richard H. F.; Ledingham, Archie E.
From Canadian Journal of Research, Section B: Chemical Sciences (1944), 22B, 115-24. Language: Unavailable,
Database: CAPLUS
SciFinder® Page 69
A description of the prepn. of several new substances that were made as intermediates in possible alternate methods of
synthesizing 2,3,4-Me(EtO)(MeO)(C6H2CHO (C. A. 36, 5825.2). Formalin (25 cc.) was boiled 30 min. with 25 g. 2,3-
(MeO)2C6H3CO2H and 40 cc. HCl. Fractional crystn. of the ether ext. of this reaction mixt. from Me2CO and from ether
gave, surprisingly, 8 g. 6,3,4-ClCH2(MeO)2C6H.CO.O.CH2 (I), m. 106°, and some bis(3-carboxy-2-hydroxymethyl-4,5-
dimethoxybenzyl) ether dilactone, m. 213°, slightly sol. in ether, Me2CO and alc., and a small amt. of meconin, m. 102°.
Redn. of 6 g. I by heating overnight with 5 g. Zn in 100 cc. alc. contg. 10 cc. HCl, with addn. of HCl until the Zn had all
reacted, gave 6,3,4-Me(MeO)2C6H.CO.O.CH2 (II), m. 127°. The structure of I and II as prepd. above was uncertain, but
was established by an independent synthesis of II described later. Reaction of 5 g. 2,3-EtO(MeO)C6H3CO2H with CH2O
and HCl gave 3 g. 3,4,6-EtO(MeO)(CH2Cl)C6H.CO.O.CH2 (III), m. 130°. Boiling III with water gave 3,4,6-
EtO(MeO)(CH2OH) C6H.CO.O.CH2, m. 120°. Addn. of 7 g. III to NaOMe (7 g. Na in 50 cc. MeOH) contg. excess HCN,
and heating of the reaction mixt. for 1 h. gave 3 g. 3,4,6-EtO(MeO.)(CH2CN)C6H.CO.O.CH2 (IV), b2 145°, m. 132°.
Sapon. of 2 g. IV by heating 24 h. with alc. NaOH, followed by acidification, gave 3,4,6-
EtO(MeO)(CH2CO2H)C6H.CO.O.CH2, m. 151°. Redn. of III with Zn-acid gave 6,3,4-Me(EtO)(MeO)C6H.CO.O.CH2(V),
m. 119°. The yield of 5,2,3-Me(HO)(MeO)C6H2CHO (VI) prepd. from creosol and CHCl3 by the method of Tiemann and
Koppe (Ber. 14, 2015-28(1881)), was inferior to that obtained by the use of Duff's aldehyde synthesis (C. A. 36, 1597.3).
Hexamethylenetetramine (25 g.) was added to a mixt. of 150 g. glycerol and 35 g. HBO3 maintained at 170°. The temp.
was allowed to drop to 160°, then 25 g. PhOH added in 1 portion and the temp. maintained at 150-5° for 15 min. The
mixt. was then cooled to 110°, 30 cc. H2SO4 in 100 cc. water added and steam-distd., whereupon 11-12 g. VI, m. 77°
(oxime m. 165°), crystd. in the condenser. Alternate addns. of Me2SO4 and 40% NaOH to VI gave 5,2,3-
Me(MeO)2C6H2CHO (VII), m. 40° (oxime, m. 99°). Condensation of VII (22 g.) with 22 g. CH2(CO2H)2 in 50 g. pyridine
contg. 2 drops piperidine by heating on the steam bath until evolution of CO2 ceased, then heating to gentle boiling and
acidifying the cooled mixt., gave 24 g. 5,2,3-Me(MeO)2C6H2CH:CHCO2H, m. 188°, which was reduced in aq. soln. with
4% Na-Hg to 5,2,3-Me(MeO)2C6H2CH2CH2CO2H. Oxidn. of 5 g. VII suspended in warm water, stirred with CO2, by
addn. of solid KMnO4, gave 3 g. 5,2,3-Me(MeO)2C6H2CO2H, m. 91°, which when heated 35 min. with CH2O and HCl,
gave a quant. yield of II. Ethylation of VI was more difficult than the methylation, but ultimately a good yield of impure
5,2,3-Me(EtO)(MeO)C6H2CHO (VIII) was obtained, which, with CH2(CO2H)2 gave 5,2,3-Me(EtO)(MeO)C6H2CH:CHCO2H
m. 168°, which was reduced to 5,2,3-Me(EtO)(MeO)C6H2CH2CH2CO2H, m. 100°. Oxidn. of VIII with aq. KMnO4 gave
80% Me(EtO)(MeO)C6H2CO2H, m. 89°, which with formalin and HCl gave, quant., 6,3,4-Me(EtO)(MeO)C6H.CO.O.CH2,
m. 119°. Acetylation of 15 g. 4,2-Me(MeO)C6H3OH with 10 g. Ac2O and a drop of H2SO4 for 1 h. at 100° gave 17 g. of
the acetylcreosol, b12 136°. With 27 g. AlCl3 in 60 cc. PhNO2, at 80° for 1 h., the acetylcreosol gave 70% 6,3,4-
Me(HO)(MeO)C6H2COMe (IX), m. 129°, and 1 g. 6,3,4-Me(HO)2C6H2COMe, (X), m. 169°. Methylation of IX or X gave,
quant., 6,3,4-Me(MeO)2C6H2COMe (XI), m. 76°. Addn. of 2.3 g. Na in 80 cc. abs. alc. to 17 g. XI and 13 g. BuNO3 gave,
after standing in the ice box for several days, the isonitroso ketone (XII), m. 122°. Heating XII with aq. NaOH until the
yellow color had nearly faded gave 6,3,4-Me(MeO)2C6H2CO2H, m. 147°. 2,3-EtO(MeO)C6H3CHO and CH2(CO2H)2
gave 2,3-EtO(MeO)C6H3CH:CHCO2H, m. 152°, which was reduced with Na-Hg to 2,3-EtO(MeO)C6H3CH2CH2CO2H, m.
64°. 2,3,4-Me(EtO)(MeO)C6H2CHO (C. A. 36, 5825.2) and CH2(CO2H)2 gave, quant., 2,3,4-
Me(EtO)(MeO)C6H2CH:CHCO2H, m. 186°, which was reduced with Na-Hg to 2,3,4-Me(EtO)(MeO)C6H2CH2CH2CO2H,
m. 121°. 3,2-EtO(HO)C6H3CHO (XIII) and Me2SO4 gave 3,2-EtO(MeO)C6H3CHO, b1 118°, which with aq. KMnO4 gave
3,2-EtO(MeO)C6H3CO2H, m. 64°. Condensation of XIII with CH2(CO2H)2 gave 3,2-EtO(MeO)C6H3CH:CHCO2H, m.
184°, which was reduced to 3,2-EtO(MeO)C6H3CH2CH2CO2H, m. 66°. 2,3,4-Me(MeO)2C6H2CHO, m. 153°
(Gattermann, C. A. 2, 820) was oxidized to 2,3,4-Me(MeO)2C6H2CO2H, m. 147° (Perkin and Weizmann, J. Chem. Soc.
89, 1649-65(1906)).
~0 Citings
131. Alkyd resin

From No Corporate Source data available (1944), JP 162641 19440308, Language: Unavailable, Database: CAPLUS
Alkyd resin, prepd. from glycerol, AcOH, anhyd. C6H4(COOH)2 and a fatty acid (2:1:2:3 in wt.) by acetylating the 1st with
the 2nd in CO2 gas below 130°, and then adding the last 2 at 180-230°, is fire-resistant and easily miscible with acetate
and nitrate fibers.
~0 Citings
132. Compounds of pharmaceutical interest from 4-methoxy-1-naphthylamine

By Bachman, G. Bryant; Wetzel, John W.
DOI:10.1021/jo01175a005
SciFinder® Page 70
Some substituted benz[c]acridines and benzo[h]quinoline derivs. are synthesized and may be useful as antimalarials. 4-
Hydroxy-1-naphthylamine-HCl, m. 265-7° (decompn.), is converted into 75% 4-acetamido-1-naphthol (I) and methylated
in 90% yield to 4-acetamido-1-methoxynaphthalene (II). II is hydrolyzed by refluxing with 1 N HCl in MeOH for 6 h. to
give 90% 4-methoxy-1-naphthylamine-HCl (III), m. 278-9° (decompn.). Neutralization of III with Na2CO3 gives 4-
methoxy-1-naphthylamine (IV). When 40 g. II is hydrogenated in 600 cc. dioxane at 130-40° and 1500-2000 lb. H
pressure in the presence of 5 g. U.O.P. Ni catalyst (V), 70-85% 4-acetamido-1-methoxy-5,6,7,8-tetrahydronaphthalene
(VI), crystals from EtOH, m. 188-9°, is obtained. Refluxing of VI with alc. HCl for 6 h. gives 95% (4-methoxy-5,6,7,8-
tetrahydro-1-naphthyl)amine-HCl, m. 250-3° (decompn.); free base (VII), m. 61°, oxidizes rapidly in air and turns purple.
An attempt to prep. VII by reducing 1-methoxy-4-nitroso-5,6,7,8-tetrahydronaphthalene failed because on nitrosation of
1-methoxy-5,6,7,8-tetrahydronaphthalene the MeO group is hydrolyzed, giving 68.5% 4-nitroso-5,6,7,8-tetrahydro-1-
naphthol (VIII), m. 161-3°. Redn. of VIII by dissolving it in concd. NH4OH and passing H2S into the filtered soln. gives
67% 4-amino-5,6,7,8-tetrahydro-1-naphthol (IX), m. 144-6° (decompn.). Acetylation of IX gives 90% 4-acetamido-
5,6,7,8-tetrahydro-1-naphthol (X), m. 188-9°. X is also obtained in 75% yield when 28 g. I is hydrogenated in 250 cc. dry
dioxane at 130° and 1400 lb. pressure in the presence of 5 g. V. Methylation of X with Me2SO4 gives VI. Ethylation of X
gives 70% 4-acetamido-1-ethoxy-5,6,7,8-tetrahydronaphthalene (XI), m. 195-6°. VII (16.5 g.) is condensed with 16.2 g.
2,4-Cl2C6H3CO2H (XII) by refluxing in 100 cc. BuOH in the presence of 12 g. K2CO3 and 0.75 g. Cu bronze 7 h., with
addn. of 1 g. K2CO3 and 0.3 g. Cu bronze after 3 h. of heating. NaOH (25 cc. 20%) is added, the BuOH removed by
steam distn., and the soln. satd. with CO2, causing the sepn. of 40% crude 4-chloro-N-(4-methoxy-5,6,7,8-tetrahydro-1-
naphthyl)anthranilic acid (XIII), m. 200-25°. XIII is cyclized by refluxing 22.8 g. in 82.5 cc. POCl3 for 4 h. After 1/2 of the
POCl3 is distd. off, the reaction mixt. is poured into a mixt. of 650 cc. ice H2O, 500 cc. concd. NH4OH, and 500 cc.
CHCl3. The CHCl3 layer is sepd., the aq. soln. repeatedly extd. with CHCl3, and the combined CHCl3 exts. are dried and
evapd., giving 39% 7,10-dichloro-5-methoxy-l,2,3,4-tetrahydrobenz[c]acridine (XIV), yellow crystals from C6H6-heptane,
m. 190-1°. Condensation of IV with XII gives 4-chloro-N-(4-methoxy-1-naphthyl)anthranilic acid (XV), m. 275-80°, which
is also obtained in 35-40% yield from III by addn. of sufficient K2CO3 to liberate IV. In these reactions, an acidic
byproduct, m. 225-42°, contg. Cl but no N, is isolated but not identified. Refluxing XV with POCl3 gives 46% 7,10-
dichloro-5-methoxybenz[c]acridine (XVI), m. 199-200°. XIV (3.32 g.) is dissolved in 10 g. PhOH at 120-5°, 1.74 g.
MeCH(NH2)CH2CH2CH2NEt2 (XVII) is added, and the mixt. heated 3 h. The hot soln. is slowly dropped into a cold mixt.
of 50 cc. ether and 50 cc. 10% NaOH, causing the sepn. of a solid, m. 335°, which seems to be the acridone formed on
hydrolysis of XIV, since on treatment with POCl3 XIV is formed. Extn. of the alk. soln. with ether and repeated crystn. of
the residue of the dried ether ext. from heptane give 10-chloro-5-methoxy-7-phenoxy-1,2,3,4-tetrahydrobenz[c]acridine,
yellow crystals, m. 193-5°. Evapn. of the heptane mother liquor gives the hydrated form, m. 90-3°, of 10-chloro-7-[(4 -
diethylamino-1-methylbutyl) amino]-5-methoxy-1,2,3,4-tetrahydrobenz[c]acridine. Because it is impossible to obtain the
anhyd. base in a cryst. form, it is converted into the di-HCl salt (XVIII). The hydrated di-HCl salt, obtained in 30% yield,
loses its H2O on prolonged heating at 140°/15 mm. over P2O5. XVIII has a transition point at 175-8° and m. 247-50°
(decompn.). Reaction of XVI and XVII in the presence of phenol gives 10-chloro-5-methoxy-7-phenoxybenz[c]acridine,
m. 182-3°. Condensation of XVI with XVII for 7 h. at 135° gives 41% 10-chloro-7-[(4-diethylamino-1-methylbutyl)amino]-
5-methoxy-benz[c]acridine-2HCl, yellow crystals with 0.5 H2O from EtOH-iso-PrOH, m. 233-5° (decompn.) with a
transition point at 215-16°. Skraup reaction by dropwise addn. of 39 cc. concd. H2SO4 to a hot soln. of 31 g. X, 70 cc.
glycerol, and 9.15 cc. PhNO2 over a period of 1 h., refluxing of the mixt. for 2 h., and pouring it onto 500 cc. ice cause the
sepn. of an acid-insol. tar which is filtered off. The filtrate is neutralized with 15% NaOH, giving a white ppt. which is
distd. at 1 mm. Recrystn. of the distillate gives 25-30% 6-hydroxy-7,8,9,10-tetrahydrobenzo[h]quinoline, plates from
EtOH, m. 257-8° (HCl salt m. 270-2° (decompn.)). Condensation of VII.HCl with Na Et ethoxalylacetate (XIX) according
to Mueller and Hamilton (C.A. 38, 3982.7) gives 93% di-Et (4-methoxy-5,6,7,8-tetrahydro-1-naphthylimino)succinate
(XX), crystals from MeOH-H2O, m. 54°. Ring closure of XX by dropping it into mineral oil, preheated to 250°, gives 75%
2-carbethoxy-4-hydroxy-6-methoxy-7,8,9,10-tetrahydrobenzo[h]quinoline (XXI), m. 212-14°. When 20 g. XXI is heated
with 500 cc. 10% NaOH on a steam bath for 2 h. and the mixt. acidified with HCl, 90% 2-carboxy analog (XXII), m. 263-
4° (decompn.), is obtained. Decarboxylation of 2 g. XXII by heating it with 0.5 g. CuO.Cr2O3 catalyst 10 min. at 250°,
extn. of the reaction mixt. with 10% NaOH, and satn. of the filtered soln. with CO2 give 60-70% 4-hydroxy-6-methoxy-
7,8,9,10-tetrahydrobenzo[h]quinoline (XXIII), m. 257-8°. Refluxing 2 g. XXIII with POCl3 2 h., distg. off of a part of the
POCl3, pouring the reaction mixt. onto ice, adding 5 cc. concd. HCl, decolorizing the mixt., and neutralizing it at 20-30°
with NH4OH give 75% 4-Cl analog (XXIV), crystals from MeOH-H2O, m. 107°. When 0.25 g. XXIV and 0.31 g.
H2NCH2CH2CH2NEt2 (XXV) are refluxed 8 h., the reaction product washed with H2O, dissolved in ether, the ether ext.
washed with 5% NaOH, extd. with HCl, and the HCl ext. made alk., 4-(3-diethylaminopropylamino)-6-methoxy-7,8,9,10-
tetrahydrobenzo[h]quinoline (XXVI) seps. as an oil and crystallizes on long standing. XXVI is isolated in 70% yield as the
di-HCl salt, very hygroscopic yellow crystals, m. 252-4° (decompn.). When III is treated with XIX according to M. and H.
(loc. cit.), 85% di-Et (4-methoxy-1-naphthylimino)succinate, yellow crystals from MeOH, m. 77°, is obtained and when
dehydrated by dropping into preheated mineral oil it gives 88% 2-carbethoxy-4-hydroxy-6-methoxybenzo[h]quinoline
(XXVII), yellow crystals from a large vol. of EtOH, m. 253-5° (decompn.), in addn. to 20% alkali-insol. product.
Decarboxylation of XXVII in the same way as XXII gives 46.5% 4-hydroxy-6-methoxybenzo[h]quinoline (XXVIII), m. 269-
70°. Treatment of XXVIII with POCl3 gives 31.5% 4-chloro-6-methoxybenzo[h]quinoline (XXIX), yellow crystals from
MeOH-H2O, m. 101-2°. When XXIX is allowed to react with XXV and the reaction product is worked up as XXVI, 70% 4-
(3-diethylaminopropylamino)-6-methoxybenzo[h]quinoline-2HCl (XXX), m. 246-8°, is obtained. Condensation of 3.37 g.
VII with 4 g. AcCH2CO2Et 16 h. at room temp. gives 70% Et β-[(4-methoxy-5,6,7,8-tetrahydro-1-naphthyl)-
amino]crotonate, m. 81-2°, which, when added slowly to mineral oil heated at 260°, gives 78.5% 4-hydroxy-6-methoxy-2-
methyl-7,8,9,10-tetrahydrobenzo[h]quinoline (XXXI), m. 273°. Refluxing 5.53 g. XXXI with 32 cc. POCl3 gives 51.5% of
the 4-Cl analog, crystals from MeOH, m. 104-5°. Only XXX shows antimalarial activity on malaria-infected ducklings.
~3 Citings

SciFinder® Page 71
133. Comparison of methods for the determination of glycerol by acetylation
By Pohle, W. D.; Mehlenbacher, V. C.
From Oil and Soap (Chicago) (1946), 23, 48-50. Language: Unavailable, Database: CAPLUS,
DOI:10.1007/BF02664432
The acetylation is performed with a reagent consisting of acetic anhydride 1 vol., in pyridine 6 vol. The method: Weigh
0.10 to 0.15 g. of sample contg. about 95% glycerol or 0.12 to 0.18 g. of sample contg. 80% glycerol into a 300-ml.
Erlenmeyer flask. Add 5 ml. of acetic anhydride-pyridine reagent. Conduct a blank, but do not heat it. Heat sample for
30 to 40 min. on steam bath, cool, and add 5 ml. distd. water and heat 1 to 2 min. Cool 10 to 15 min. at room temp. and
add 25 ml. of isobutyl alc. and titrate with alc. KOH, 0.32 to 0.35 N, using phenolphthalein as indicator. The av. of 17
analyses was 94.97% glycerol and the standard deviation was ±0.3%.
~0 Citings
134. The phosphoric diesters obtained from 2-chloroethyl dichlorophosphate and glycerol
By Darmon, M.
From Bulletin de la Societe Chimique de France (1947), 262-6. Language: Unavailable, Database: CAPLUS
ClCH2CH2OPOCl2 (I), prepd. from HOCH2CH2Cl and POCl3, b12 103° (cf. C.A. 31, 4646.2). I (19.8 g.) and 9.2 g.
glycerol were heated at 100°; HCl was evolved and the last traces removed in vacuo. The residue was a thick
homogeneous oil that could not be distd. at 2 mm. (resinification). Its mol. wt. in camphor was 300-89 (concns. 2-18%;
calcd. for monomer, 216, dimer 432). The oil was treated with a slight excess of satd. Ba(OH)2 soln. and then with the
calcd. amt. of AgNO3 to remove Cl ions present; concn. almost to dryness gave crystals of Ba(NO3)2 and an oil; the latter
and EtOH at 95° gave 2 fractions: an insol. viscous oil (II) and a sol. thick colorless or light yellow oil (III). II was dried
with difficulty at 110° to a fine white powder but easily absorbed H2O to form an oil again. III was identified as
[ClCH2CH2OPO2OCH2CH(OH)CH2OH]2Ba, and II as [ClCH2CH2OPO2OCH2CH(OH)CH2OPO2OCH2CH(OH)CH2OH]Ba,
from the following data: Free OH groups detd. with C5H5N-Ac2O (as g. substance per OH group): II 166-180 (174.5
calcd.); III 144 (151 calcd.). Mol. wt. in freezing H2O: II 214-222 (calcd. 262); III 162-8(calcd. 201). Acetylation with Ac2O
and HOAc at reflux for 3-4 h. gave a colored powder with II and a very viscous oil with III; mol. wt. in camphor of the
acetate: II 315-18 (325 calcd.); III 240-4 (257 calcd.). Both II and III with HIO4 consumed 1 atom O, so the -
OCH(CH2OH)2 grouping cannot be present. Ethylene oxide (IV) was found in the reaction mixt. of I and glycerol in a
concn. of 2% (3% calcd.) by the pyridine color test (cf. C.A. 33, 7238.3), confirming the hydrolysis mechanism of the
ester grouping to form IV and Cl-: with breaking of the O-P linkage rather than the C-O linkage (cf. C.A. 33, 8564.9).
Et3PO4 (V), prepd. from POCl3 and 3 mols. NaOEt in anhyd. Et2O, b30 102-3°. Di-Et 2-chloroethyl phosphate (VI),
obtained by refluxing I and 2 mols. anhyd. EtOH in CCl4 2 h., b4.5 118-19°. Mol. wt. of V in camphor, 149-193 (182
calcd.); of Ph phosphate (m. 49.5°), 306-326 (326 calcd.); of VI, 207-224 (216.5 calcd; 2.5-23% concn.).
~1 Citing
135. The oil of the cotía chestnut. II. Extraction, physical and chemical characteristics
By Cavalcanti, Maria da Conceicao Paes Barreto
From Revista de Quimica Industrial (Rio de Janeiro) (1947), 16(No. 180), 16-18. Language: Unavailable, Database:
CAPLUS
cf. C.A. 41, 7771b. Addnl. characteristics of the oil are: color (Lovibond) pale yellow 3, red 0.8; odor similar to that of
oiticica oil, rotation (100-ml. tube) +0.692°; abs. viscosity in poise 25° 1.40; acid no. (KOH) 3.26; acidity (oleic acid)
1.63%; index of neutralization 196.71, Hehner index 95.31; ester no. 184.24; glycerol (calcd.) 9.95%, Ac no. 139.9;
sapon. no. of the acetylated oil 327.4; Crismer index (closed vessel) 127°; Valenta index 107°; gelatinization time up to 4
hrs.; m.p. of the fatty acids (capillary) 40.2°. Drying tests proved the oil equal to oiticica and tung oil. The cake left after
expressing the oil from the almonds was extd. with ether, giving 27.10% oil (referred to the cake) and then analyzed: ash
8.71, moisture 10.24, cellulose (König) 23.00, fatty substance 17.58, crude protein (6.25 × % N) 29.44, carbohydrates (by
difference) 11.03%. Its use as fertilizer, like the linseed-oil cakes, is suggested, but use as animal food can be decided
only after the toxicology test, which could not be carried out for lack of substance.
~0 Citings
136. Glykresin (glycerol o-tolyl ether, Myanesin, BDH 312)

By Morch, P.
From Archiv for Pharmaci og Chemi (1947), 54, 327-32. Language: Danish, Database: CAPLUS
SciFinder® Page 72
Berger and Bradley (C.A. 41, 2166b) have shown that α, β-dihydroxy-γ-(2-methylphenoxy)propane (I) produces a
curarelike effect in that it causes relaxation of muscles and paralysis. Because little chem. information about I is
available, it has been synthesized and examd. more thoroughly in this work. The method of Wheeler and Wilson (C.A.
37, 3449.8) for the synthesis of α-phenyl ethers of glycerol was employed. The yield was 67%. I, m. 69-70° (cor.), is
colorless, cryst., almost without odor, and has a bitter taste. It produces numbness of the tongue. I is easily sol. in EtOH
and propylene glycol. At 20° one part is sol. in 85 water, 11 ether, 60 5% urethan soln., 40 10% urethan soln. and 4.5
25% urethan soln. Upon heating it melts first to a colorless liquid which then volatilizes with the formation of a brown
color and irritating vapors. In 10 drops concd. H2SO4 0.01 g. I has a faintly red color; addn. of one drop HCHO soln.
produces a deep red. An aq. soln. of I does not give a color reaction with FeCl3. I can be detd. by acetylation and
subsequent sapon., or by the bromometric method of Gjaldbaek and Jensen (C.A. 32, 7665.8). It appears that 2 atoms
of Br are taken up immediately by I, after which the bromination continues slowly. A bromination time of 5-10 sec. seems
best. One ml. 0.1 N KBrO3 is equiv. to 0.009111 g. of I. To det. I by the acetylation and sapon. method, mix 1-1.4 g. I in
an Erlenmeyer flask with 10 ml. Ac2O and 2 g. anhyd. AcONa, boil 1 hr. under reflux, add 50 ml. H2O through the
condenser and continue the boiling for 15 min., cool, add 10 drops phenolphthalein soln., exactly neutralize the liberated
AcOH with NaOH, add 20 ml. N NaOH, reflux for 30 min., cool, and back-titrate with N HCl. Run a blank simultaneously.
One ml. N NaOH equals 0.09111 g. I. A 1% aq. soln. of I can be autoclaved for 20 min. at 120° in sealed ampuls without
decompn.
~1 Citing
137. Acridine syntheses and reactions. III. Synthesis of aminoacridines from formic acid and amines
By Albert, Adrien
DOI:10.1039/jr9470000244
SciFinder® Page 73
cf. C.A. 36, 477.8. By using the optimum conditions for the conversion of m-C6H4(NH2)2 to proflavine, no acridines were
obtained from PhNH2, p-C6H4(NH2)2, m- or p-MeC6H4NH2, m-MeOC6H4NH2, m-ClC6H4NH2, m-O2NC6H4NH2, m-
H2NC6H4CO2H, and m-H2NC6H4SO3H; no improvement resulted by increasing the time and temp. (4 h. at 200°) or by
using 0-2 mol HCl per mol amine. The failure of m-MeC6H4NH2 and m-MeOC6H4NH2 to give acridines with HCO2H
reveals that a high electron d. ortho to an NH2 group is a prerequisite for this reaction; thus, the main usefulness of the
reaction will be confined to m-diamines. The std. conditions used in this work consisted in heating 0.1 mol amine, 0.05
mol anhyd. HCO2H, 0.115 mol HCl (as concd. HCl), and glycerol (3 times the wt. of the amine) to 155° during 0.5 h. and
maintaining this temp. for a further 0.5 h. m-HOC6H4NH2 gives 5% 3,6-dihydroxyacridine (C.A. numbering) (I) (as HCl
salt), sepd. by boiling the initial ppt. with 0.5 N HCl; neutralization of the filtrate from I with NaHCO3 and extn. with 100
parts 75% EtOH give 40% of the complex of I and 3-amino-6-hydroxyacridine, C13H9O2N-2-C13H10ON23H2O, orange,
does not m. at 350°; it can be diazotized and coupled with 2-C10H7OH (red). m-HOC6H4NEt2 (use of 0.5 the quantity of
acid and heating 1.25 h. at 155°) gives 55% pyronine B (a new xanthene synthesis). m-H2NC6H4NMe2 (II) (15 g.), added
to 20 g. ZnCl2 in 40 g. C3H5(OH)3 at 130°, followed by 14 g. (CO2H)2.2H2O, the mixt. raised to 155° during 0.5 h. and
the temp. maintained 0.75 h., the product dild. with 90 mL. boiling H2O, poured into excess NaOH, and the ppt. extd. with
EtOH, gives 3% 3,3'-bis(dimethylamino)öxanilide (III), cream, m. 203° (cor.); the filtrate yields 60% 3,6-
bis(dimethylamino)acridine (acridine orange). II (2 mol) and (COCl)2 in 5 mol C5H5N at 0° give 50% III; III could not be
acetylated and was hydrolyzed only slowly by boiling alkalies. 3-H2NC6H4NHPh (std. conditions plus 0.5 h. at 175°)
gives 40% 3,6-bis(phenylamino)acridine-HCl, scarlet, does not m. at 365°; the orange solns. show orange fluorescence
in UV light; the solns. of the free base are yellow and show green fluorescence; a byproduct is 3-aminoacridine. 2,6-
(H2N)2C6H3Me (std. conditions plus ZnCl2 and heating 5 h. at 155°) gives 57% 3,6-diamino-4,5-dimethylacridine (IV), m.
173° (cor.); it forms a bright yellow solvate with Me2CO; it is sol. in 18 parts boiling C6H6 and 14 parts boiling EtOH (poor
gradients); the EtOH soln. has a green fluorescence in daylight and a yellow in Wood's light. The orange-red HCl salt is
very sol. in H2O and the soln. has a green fluorescence. If the condensation time is 1 h., the yield of IV is 50%; with
0.55, 0.85, 1, 1.3, and 1.45 mol HCl the yields are 31, 38, 50, 53, and 45%, resp. With Ac2O IV.HCl gives the 6-AcNH
compd., yellow, m. 259-62° (decompn.); it is very sol. in H2O and the orange soln. shows no fluorescence; the yellow
diazo soln. gives a dark red color with 2-C10H7OH. 3,5-(H2N)2C6H3NH2 (std. conditions plus 0.5 h. at 175°) gives 20%
3,6-diamino-1,8-dimethylacridine, brownish yellow, m. 294-5°; the yellow solns. have a green fluorescence; the orange
soln. of the HCl salt develops a green fluorescence on diln.; the violet diazo soln. gives a red color with 2-C10H7OH; pKa
is 10.1 in 50% EtOH at 20°. 3,5-(H2N)2C6H3OMe (b0.5 198°, m. 66°) is demethylated during the condensation and yields
an intractable mixt. 3,5-(H2N)2C6H3CO2H.2HCl (4.5 g.), 2.04 g. HCO2Na, 12 g. C3H5(OH)3, and 2 mL. H2O, heated to
155° during 0.5 h., to 185° in an addnl. 0.5 h., and held at 185° for 0.75 h., give 65% 3,6-diamino-1,8-acridinedicarboxylic
acid(?), orange, does not m. at 365°; the di-Na salt forms a gel in cold H2O; the acid could not be esterified with MeOH-
HCl or decarboxylated at 365° or with Cu in boiling Ph2O or quinoline. 2,4-(H2N)2C6H3Me (std. conditions and 0.5 h. at
175°) gives 72% 3,6-diamino-2,7-dimethylacridine, m. 325°, sol. in 20 parts 0.25 N lactic acid. 2,4-(H2N)2C6H3OMe (std.
conditions plus 0.5 h. at 175°, which doubles the yield) gives 20% 3,6-diamino-2,7-dimethoxyacridine, with 1/3 mol. H2O,
yellow, m. 244°; the brown EtOH soln. has an intense yellow fluorescence; the orange HCl salt is sparingly sol. in H2O
with an intense green fluorescence and is completely pptd. by Cl ions; the red diazo soln. gives a scarlet color with 2-
C10H7OH. 2,4-(H2N)2C6H3OEt gives 20% 3,6-diamino-2,7-diethoxyacridine, pale yellow, m. 238°; the EtOH soln. has an
intense green fluorescence (cf. Brit. patent 248,182, C.A. 21, 593); the orange aq. soln. of the HCl salt has a green
fluorescence when very dil. and foaming properties which persist on diln.; it is pptd. by 0.5 N HCl; the colorless diazo
soln. couples with 2-C10H7OH (scarlet). 1,3,4-(H2N)2C6H3Cl (std. conditions with ZnCl2 and heating 3 h. at 155°) gives
35% 2,7-dichloro-3,6-diaminoacridine, orange-yellow, decomp. above 300°; heating at 175° causes resinification; its
solns. have a green fluorescence as do dil. solns. of the HCl salt; the colorless diazo soln. gives a scarlet color with 2-
C10H7OH; a byproduct is 2,2',7,7'-tetrachloro-3,3',6,6'-tetraamino-9,9',10,10'-tetrahydro-9,9'-diacridyl ether, yellow. 4,2-
H2N(Me2N)C6H3Me (std. conditions plus 0.5 h. at 175°) gives 20% 3,6-bis(methylamino)-2,7-dimethylacridine, yellow, m.
308-9°; the EtOH soln. has an intense green fluorescence. The orange HCl salt has a green fluorescence in dil. aq. soln.
and is readily pptd. by Cl ions. The loss of 2 N-Me groups may be connected with the serious clashing of van der Waals
radii (N-Me with C-Me). Unsuccessful attempts were made to condense 2 different amines under the std. conditions (m-
H2NC6H4NHOCH (or m-C6H4(NH2)2 plus HCO2H) with PhNH2.HCl or p-C6H4(NH2)2.2HCl, and also PhNHOCH with m-
C6H4(NH2)2.2HCl); in each case proflavine was the only acridine formed (usually in good yield), thus demonstrating the
mobility of the OCH group under the exptl. conditions; similar results were obtained when substantially anhyd. conditions
were used. A repetition of the conditions of Ger. patents 149,409-10(1903) and 161,699(1905) did not give the reported
results; however if 1 of the reactants is a m-H2NC6H4OH, the conditions are more favorable. 2,4-H2N)2C6H3Me.2HCl
(1.95 g.), 1.78 g. 1,3-(HCONH)2C6H3Me, 1.67 g. m-Et2NC6H4OH, and 10 g. anhyd. C3H5(OH)3, heated to 155° during
0.5 h. and the temp. maintained 1.5 h., give 25% acridine yellow and 14% 3-amino-6-diethylamino-2-methylacridine,
orange, m. 216-17°; the orange HCl salt is sol. in HCl of all concns. and the solns. have only slight fluorescence in
daylight; HNO2 gives an intense blue stable soln. which couples with 2-C10H7OH (scarlet). 2,4-Me2N(H2N)C6H3Me.2HCl
(2.33 g.), 1.5 g. 2,4-H2N(HCONH)C6H3Me, and 8 g. C3H5(OH)3, heated to 155° during 1 h., maintained at 155° for 0.5 h.,
and at 175° for 0.5 h., give 35% acridine yellow and 20% 3-amino-6-methylamino-2,7-dimethylacridine, yellow, m. 264°
(cf. Ger. patent 292,848, C.A. 11, 1908); the EtOH solns. have an intense green fluorescence; the orange acetate is very
sol. in H2O; the di-HCl salt is sol. in 3 N HCl from which it is partly pptd. as the HCl salt on diln. to 0.5 N; solns. of the
salts fluoresce intensely green when dil. and give with HNO2 violet solns. which couple with 2-C10H7OH (red). 2,4-
O2N(NH2)C6H3Me (15 g.), 10 mL. HCO2H, and 50 mL. PhMe, heated about 2 h., give a quant. yield of 2-nitro-4-
formamidotoluene, m. 133-4°; catalytic redn. in EtOH over Raney Ni at atm. temp. and pressure gives 85% 2-amino-4-
formamidotoluene, m. 113-14°.
~0 Citings

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138. The pharmacological properties of some 2-substituted 4-hydroxymethyl-1,3-dioxolanes
By Berger, F. M.; Boekelheide, V.; Tarbell, D. S.
From Science (Washington, DC, United States) (1948), 108, 561-2. Language: Unavailable, Database: CAPLUS,
DOI:10.1126/science.108.2812.561
Preliminary examn. of over 50 2-substituted 4-hydroxymethyl-1,3-dioxolanes showed that physiological action was
influenced by groups in position 2. Some of 2-alkyl and 2,2-dialkyl derivs. possessed action similar to monoethers of
glycerol. Paralyzing action appeared optimal if 6-8 carbons were attached at position 2; the lower, water-sol. members of
the series and higher, water-insol. members were inactive. The presence of free hydroxyl groups seemed to be essential
for activity; removal or acetylation markedly decreased activity.
~0 Citings
139. Strychnos alkaloids. XXXI. Further syntheses in the 5,6(N)-pyrroquinoline series

By Huisgen, Rolf.
From Justus Liebigs Annalen der Chemie (1948), 559, 174-90. Language: Unavailable, Database: CAPLUS
SciFinder® Page 75
cf. C.A. 40, 5438.4; 42, 6783i. Despite previous results, H. systematically prepd. a series of alkyl-substituted
pyrroquinolines in the hope of shedding further light on the structure of vomipyrine (I). The Hopkins-Cole color reaction
carried out with these new products led to the conclusion that the pyrrole nucleus in I must be unsubstituted. New
homologs of 5,6(N)-pyrroquinoline (II) were prepd. When the alkyl groups were to be substituents of a benzene ring, a
suitably substituted p-nitroaniline deriv. was used as mother substance. Me substitution in position 10 of II involved the
action of fused ZnCl2 on the appropriate acetone quinolylhydrazone. Nearly quant. yields of 11-alkyl-substituted derivs.
of II were formed by cyclization of the corresponding α-ketonic acid hydrazone with concd. HCl, followed by
decarboxylation. To introduce alkyl groups into the pyridine nucleus of II, the Skraup synthesis was appropriately
modified. Absorption spectra of the HCl salts of the various alkyl derivs. of II were compared with that of I.HCl, and the
colorimetric detn. of the yellow color of the various salts showed clearly the auxochrome and bathochrome effects of
each of the alkyl groups on the Ph or pyrrole nucleus. Introduction of an alkyl substituent on the pyrrole ring caused a
shift in the absorption max. of over 420 mµ, an effect which, even in the case of polyalkyl substituents, is so unequivocal
that an Et substituent in position 11 in I appears to be out of the question. Alkylation of the pyridine nucleus in II leads to
a decrease in the color of the HCl salts. The data indicate that the similarity in UV absorption of I and of II is no index
whatsoever regarding similarity of structure. Full tabulated data are given for the Hopkins-Cole reaction as applied to I,
hydroxyvomipyrine, and the various new alkyl derivs. of II. The tests indicate that I is not identical with any of the derivs.
of II synthesized by H. Some data are also given for the no. of moles of AcOH obtained when various alkyl derivs. of II
are oxidized with CrO3-H2SO4. On acetylation, followed by nitration, 2,3-xylidine gave rise to 63% 4-nitro-2,3-xylidine,
yellow prisms, m. 116°, 19 g. of which, when carried through the Skraup synthesis, yielded 13.3 g. 6-nitro-7,8-
dimethylquinoline, needles from CHCl3-EtOH, m. 137° (colorless HCl salt), which on redn. with SnCl2 and HCl gave 97%
6-amino compd. (III), colorless leaflets from C6H6, m. 163° (yellow HCl salt; Ac deriv., m. 222°). On diazotization and
redn., III gave the 6-hydrazino compd. m. 149° (isolated through its yellow HCl salt) which yielded the corresponding
yellow substituted hydrazone of PrCOCO2H, m. 201° (decompn.), cyclization of 4 g. of which yielded 1.14 g. 7,8-
dimethyl-11-Et deriv. of II, silky needles, m. 214°, subliming in a high vacuum at 140°, showing a marked UV
fluorescence in Me2CO, giving a strong bluish green Hopkins-Cole reaction (HCl salt, orange-red needles), and
hydrogenated to a tetrahydro deriv., pale yellow oil, b. 130° (in a high vacuum) [colorless HCl salt, m. 315° (decompn.)],
and giving a wine-red Hopkins-Cole reaction. 8,9-Dimethyl-11-Et deriv. (IV) of II, m. 90° (from Et2O-petr. ether), was
prepd. by the following steps: 3,6-O2N(H2N)C6H3Me → 66% 6-nitro-8-methylquinoline, needles from alc., m. 127-8° →
95% amino deriv. (V), prisms from C6H6, m. 125° 4-MeC6H4SO2Cl → 6-p-tolylsulfonamido-8-methylquinoline (97%), m.
101° (from alc.) NaOH+Me2SO,4 → 93% 6-(N-methyl-p-tolylsulfonamido)-8-methylquinoline, m. 112° H2SO4 followed
byNaOH → 6-methylamino-8-methylquinoline (isolated as a cryst. hydrate or as the oily base), b0.1 110° → 95% colorless
6-(methylnitrosamino) deriv., C11H11ON3, b0.1 140°, m. 86° Al-Hg → 8% 6-(1-methylhydrazino)-8-methylquinoline (isolated
as the HCl salt) → substituted hydrazone of PrCOCO2H, yellow, m. 220° (orange-red HCl salt) ZnCl2 → 92% IV. When
mixed with I, IV sintered at 63° and m. 70°, thus clearly indicating that I and IV are not identical. 4-O2NC6H4NH2 (VI) (20
g.) was treated with 20 cc. paraldehyde and 32 cc. HCl, and after controlling the original exothermic reaction, refluxed 2
h., poured into NH4OH at 0°, filtered, the resulting ppt. heated with 3 N HCl, and the soln. bone-blacked, filtered, made
alk. with NH4OH, extd. with CHCl3, and filtered through Al2O3, giving 11.7 g. (43%) 6-nitro-2-methylquinoline (VII)
colorless, m. 165° (from 80% MeOH). No improvements in the yield of VII were noted when As2O5 was used in the
original reaction mixt. On redn. VII gave the 6-amino deriv., long needles from 65% EtOH, m. 187°, from which was
formed 6-hydrazino-2-methylquinoline, colorless needles, m. 156° (pale yellow HCl salt). Heating 8.5 g. VI in a mixt. of 5
mL. abs. alc., 3 g. AcCH2CH2Cl, and 10 g. SnCl2.3H2O 3 h., pouring the mixt. into an excess of 30% NaOH, dissolving
the product in 3 N HCl, and purifying by extn. with CHCl3, etc. (as above), gave 1.8 g. 6-nitro-4-methylquinoline, m. 130°
(from EtOH) (colorless HCl salt); 6-NH2 compd., colorless rods from 50% MeOH, m. 171°; 6-hydrazino compd., colorless,
m. 146° (pale yellow HCl salt). Twice the theor. amt. C2H4 was passed into a mixt. of 80 g. AlCl3, 60 mL. CS2, and 45 g.
EtCOCl at 0°, the mixt. extd. with Et2O, and the ext. neutralized by shaking with NaHCO3, dried, and distd. in vacuo, thus
giving 11.4 g. 1-chloro-3-pentanone, b22 65°, which reacted with 2,5-H2N(O2N)C6H3Me in the usual way to give 29% 6-
nitro-4-ethyl-8-methylquinoline, coarse crystals from MeOH, m. 129°; NH2 compd., colorless needles, m. 145°, whose
diazonium salt gave the 6-hydrazino compd., isolated as the pale orange HCl salt. Analogously prepd. were 6-nitro-4-
ethyl-7-methylquinoline (18%), m. 117° (from MeOH), the NH2 compd., m. 162° (from MeOH), and the hydrazino compd.,
m. 176° (pale yellow HCl salt, decompg. about 260°). 6-Hydrazino-8-methylquinoline (prepd. from V) m. 141° (from
C6H6) (orange-yellow HCl salt). Indole cyclization to form those alkyl derivs. of II which were not substituted in positions
10 and/or 11 was effected by treating the appropriate hydrazone of MeCOCO2R with ZnCl2. Thus prepd. from 6-
hydrazino-7,8-dimethylquinoline, the pyruvic acid hydrazone, orange-red needles, decompg. 200°, gave an Et ester, m.
104° (H2SO4 salt, lemon-yellow), which, when cyclized with ZnCl2 at 240-70°, evolved CO2 and C2H4, giving the 7,8-di-
Me deriv. of II, colorless polyhedrons (from Me2CO). Similarly the following alkyl derivs. of II were prepd.: 8-Me, hone-
shaped crystals from Me2CO, m. 185°; 2-Me, rods from Me2CO, m. 220°; 4-Me, colorless polyhedrons from Me2CO, m.
228°; 4-ethyl-7-Me, fine needles from Me2COCHCl3, m. 217° (pale yellow HCl salt); 4-ethyl-8-Me, rod lets from Me2CO,
m. 166°. In order to obtain 10-substituted derivs. of II, the appropriate hydrazone of Me2CO was similarly cyclized. Thus
H. prepd. the following derivs. of II: 10-Me, colorless polyhedrons from Me2CO, m. 198°; 2,10-di-Me, m. 166° (from
Me2COC6H6) (HCl salt, silky golden needles): 4,10-di-Me, colorless polyhedrons from aq. Me2CO, m. 207°; 7,8,10-tri-Me,
colorless leaflets from MeOH, m. 177-8°; 4-ethyl-7, 10-di-Me, needles from Me2CO-Et2O, m. 182°; 4-ethyl-8,10-di-Me,
leaflets from Me2CO-Et2O, m. 196°. In the case of the 11-substituted derivs. of II, the cyclization of the appropriate
hydrazones of α-keto acids was effected more satisfactorily with aq. HCl than by using ZnCl2. Thus 1 g. of the 6-
quinolylhydrazone of MeCH2COCO2H, orange-yellow, m. 190° (decompn.), gave the 11-methyl-10-carboxy deriv. of II,
microcrystals, m. 265°, which in vacuo at 250° lost for CO2, forming quant. the 11-Me deriv. of II, coarse long needles
(from Me2CO), m. 196°. Similarly, the orange-red 8-methyl-6-quinolylhydrazone of MeCH2CH2COCO2H, m. about 200°
(decompn.), yielded the 8-methyl-10-carboxy-11-Et deriv. of II, m. 243° (from MeOH), which when decarboxylated at 12
mm. and 240° gave the 8-methyl-11-Et deriv. of II, polyhedrons, m. 175° (from MeOH). Cyclization of the substituted
hydrazones of cyclohexanone or MeCOEt is effected readily by the use of mineral acids, AcOH, or NiCl2. Thus 1 g. 6-
hydrazinoquinoline-HCl, 3 cc. AcOH, and 1 cc. cyclohexanone yielded 70% of the 10,11-tetramethylene deriv. of II, m.
239° (from EtOH) (red HCl salt), which was dehydrogenated to the pyridocarbazole deriv., C17H14N2, needles from
SciFinder® Page 76
MeOH, m. 271°, whose HCl salt was less colored than that of the parent substance. The following derivs. of II were also
prepd.: 7,8,10,11-tetra-Me, needles from EtOH, m. 201°; 2-methyl-10,11-tetramethylene, m. 211°; 2,10,11-tri-Me, m.
186° (from aq. Me2CO); 8,10,11-tri-Me, m. 188°; and 4-methyl-10,11-tetramethylene, needles from 80% MeOH, m. 220°.
~1 Citing
140. Quantitative studies on the partial enzymic hydrolysis of triglycerides

By Desnuelle, P.; Naudet, M.; Rouzier, J.
From Biochimica et Biophysica Acta (1948), 2, 561-74. Language: French, Database: CAPLUS
cf. C.A. 41, 93a; 42, 7349e. The techniques developed to differentiate quantitatively between glycerol, mono-, di- and
triglycerides are as follows: to each 8 cc. of hydrolytic medium are added 1.3 cc. glacial AcOH and 65 cc. of a 1:1 alc.:
ether soln. The mixt. is warmed, the coagulated proteins are filtered off, they are washed twice with 10 cc. portions of
alc.:ether, and the filtrate is concd. below 50° to 10 cc. The soln. is treated with 40 cc. ether, the phases are sepd., and
the ethereal phase is washed 3 times with 10 cc. portions of water, then the combined water phases are washed twice
with ether. The ether soln. is evapd., treated with 10-cc. portions of water and evapd. below 50° to remove all AcOH.
The dry residue is taken up in a known vol. of ether. An aliquot of the ether soln., contg. about 0.04 millimoles of α-
monoglyceride, is added to 1.5 cc. of a 1:2 AcOH:CHCl3 mixt. and 4 cc. of periodate soln. The latter consists of 0.5 g.
Na metaperiodate in 20 cc. water and 100 cc. AcOH. After 15 min. at room temp. 4 cc. of AcOH and 3 cc. of 10% KI are
added and the mixt. is titrated with 0.09 N Na2SO3. An ether aliquot is titrated for its free fatty acid content with 0.02 N
alc. KOH in a mixed solvent composed of 1 part ether, 1 part 96% alc., and 2 parts CHCl3. The total ether sol. OH
groups are detd. in an aliquot contg. 0.5-2.0 milliequivs. of OH, by adding 2 cc. of acetylating agent (6.25 g. acetic
anhydride added to 25 cc. anhyd. pyridine) and heating for 1 hr. at 100-105°. After cooling 1 cc. water and 5 cc. pyridine
are added, the mixt. is heated again at 100-105° for 20 min., cooled and partially neutralized with exactly 25 cc. of 0.4 N
alc. KOH. The final titration is made with 0.1 N alc. KOH to a permanent pink coloration with phenolphthalein. The
difference in titrations between an identical blank treatment and the unknown gives the OH value. The free glycerol of
the original aq. phase is detd. colorimetrically by the method of Desnuelle, et al. (Trav. membres soc. chim. biol. 26,
1168(1944)). Mono-oleinglyceride was found to be separable as follows: 0.5 g. of fat in ether are mixed with 200 g.
defatted sand and the ether carefully evapd. Through this mixt. are slowly passed 200 cc. of 60% alc. The effluent is
dild. to 40% alc. concn., then extd. 4 times with 75 cc. portions of petr. ether. The exts. are evapd. below 50° and the
residue weighed. A synthetic mixt. contg. 66.4 mg. mono-α-oleinglyceride, 174.7 mg. oleic acid and 307.9 mg. di- and
tri-oleinglycerides was treated as described, and the petr. ether residue analyzed for the added constituents. None of the
di- and tri-oleinglycerides were in the petr. ether, while 59.8 mg. of mono-α-oleinglyceride and 108.0 mg. oleic acid were
recovered. Synthetic trioleinglyceride in 0.1 M phosphate and in the presence of small amts. of bile salts at 37° is
hydrolyzed in 4 hrs. by pancreatin at pH 7.0 in the absence of Ca salts primarily to diglycerides with large amts. of
unreacted triglycerides remaining, and only small quantities of monoglycerides and traces of free glycerol detectable. At
pH 8 the results are analogous except that smaller amts. of unreacted triglycerides remain. At pH 8 in the presence of
one Ca ion for each potential fatty acid chain tri- and diglycerides hydrolyze completely to monoglycerides.
~1 Citing
141. Preparation and properties of some cyclic esters of phosphorous acid

By Arbuzov, A. E.; Zoroastrova, V. M.; Rizpolozhenskii, N. I.
From Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1948), 208-18. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 77
Reaction of PCl3 with (CH2OH)2. MeOCH2CH(OH)CH2OH, 1,3-butanediol, (CH2CH2OH)2 and O(CH2CH2OH)2 in dry
Et2O in the presence of pyridine or PhNMe2 gave resp.: CH2.CH2.O.PCl.O, b10 41.5°, d20 0 1.4172, n20 D 1.4915;
MeOCH2CH.CH2.O.PCl.O b9 78.5-79.2°, d20 0 1.2984, n20 D 1.4722; MeCH.CH2.CH2.O.PCl.O, b12 65°, d20 0 1.2496, n20
20 20
D 1.4765; CH2.CH2.CH2.CH2.O.PCl.O, b8 74-5.5°, d 0 1.2858, n D 1.5010; and CH2.CH2.O.CH2.CH2.O.PCl.O, b15
104-5°, d20 0 1.2693, n20 D 1.5165. The products were isolated by filtration of the base-HCl, followed by distn. in vacuo.
The yields of 5- and 6-membered ring derivs. were good, others were considerably poorer; the former are colorless,
reactive liquids, fuming in air; the 6-rings are more stable than the 5-rings. Derivs. with 7 or 8 atoms in the ring are very
unstable, fume in the air, and burn when poured on a filter paper; even in sealed tubes these, originally mobile colorless
liquids, polymerize, on standing, into yellowish gels. All of the cyclic compds. listed above give neutral esters of H3PO3
with dry ROH in the presence of pyridine or PhNMe2; the same products are more readily obtained by reactions of
ROPCl2 with the corresponding glycols. The following were prepd. (no yields given): CH2.CH2.O.P(OMe).O, b23 55-6°,
d20 0 1.2159, n20 D 1.4460; CH2.CH2.O.P(OEt).O, b15 51.5°, d20 0 1.1317, n20 D 1.4395; CH2.CH2.O.P(OBu).O, b8.5 71-2°,
d20 0 1.0819, n20 D 1.4470; CH2.CH2.O.P(OCH2CH2Cl).O, b6.5 78.5-9.5°, d20 0 1.3206, n20 D 1.4755;
MeOCH2CH.CH2.O.P(OMe).O, b9 77-8°, d20 0 1.1798, n20 D 1.4459; MeOCH2CH.CH2.O.P(OEt).O, b10 84-5°, d20 0
1.1415, n20 D 1.4498; MeOCH2CH.CH2.O.P(OBu).O, b9 107-7.5°, d20 0 1.0713, n20 D 1.4450;
MeOCH2CH.CH2.O.P(OPh).O, b7 145.5-6°, d20 0 1.2130, n20 D 1.4768; EtOCH2CH.CH2.O.P(OEt).O, b7 93-4°, d20 0
1.0937, n20 D 1.4401; ClCH2CH.CH2.O.P(OBu).O, b8 108.5-10°, d20 0 1.1629, n20 D 1.4601;
MeCH.CH2.CH2.O.P(OMe).O, b13 62°, d20 0 1.1092, n20 D 1.4420; MeCH.CH2.CH2.O.P(OEt).O, b8 63-4°, d20 0 1.0696,
n20 D 1.4410; CH2.CH2.CH2.CH2.O.P(OMe).O, b4.5-5 54-5°, d20 0 1.1640, n20 D 1.4642; CH2.CH2.CH2.CH2.O.P(OBu).O,
b9-10 100-2°, d20 0 1.0557, n20 D 1.4540. These are analogous to (RO)3P in their reactions and are rapidly oxidized by
HNO3, frequently with flames. All react with water with evolution of much heat. The following CuX adducts were
obtained in solid state: CH2.CH2.O.P(OMe).O.CuI, m. 132-3°; CH2.CH2.O.P(OEt).O.CuI, m. about 90°;
CH2.CH2.CH2.O.P(OEt).O.CuI, m. 135°; CH2.CH2.CH2.CH2.O.P(OMe).O.CuI, m. 142-4°. Addn. of S (considerable heat
evolution) similarly gave MeOCH2CH.CH2.O.PS(OMe).O, b1.5 111-12.5°, d20 0 1.2877 n20 D 1.4889; similar addn. to the
EtO analog was sluggish and required heating to 110-20°; the product MeOCH2CH.CH2.O.PS(OEt).O, b2 121.5-22°, d20
20
0 1.2359, n D 1.4790. The trivalent nature of the above esters is readily established by their reaction with halides. In
such reactions, some of the cyclic esters suffer ring opening, others retain the ring structure, while in some cases the
type of reaction depends on the reagent used. In no instance was a simultaneous occurrence of both of the above
reaction courses observed, although the low yields of isolated products preclude a positive statement in this respect.
The most characteristic reaction of cyclic esters from HOCH2CH2OH is the ease of opening of the 5-membered ring,
C.C.O.P.O. Thus, CH2.CH2.O.P(OEt).O and EtBr give Et(BrCH2CH2O)P(O)OEt, b11 129-30°, d20 0 1.3726, n20 D 1.4610;
similar reaction with PhCH2Cl gave PhCH2(ClCH2CH2O)P(O)OEt, b7.5-8 182-3°, n20 D 1.5128; while reaction with Ph3CBr
gave Ph3C(BrCH2CH2O)P(O)OEt, m. 99-101°, which on hydrolysis with HCl gave Ph3CPO3H2. Reaction of
CH2.CH2.O.P(OMe).O with Ph3CBr gave Ph3C(BrCH2CH2O)P(O)OMe, m. 153-5°, which on hydrolysis also gave
Ph3CPO3H2. Due to unavailability of MeCH(OH)CH2OH, the other 5-membered ring system was based on glycerol (1-
ethers). The compds. derived from these were shown to have a stable 5-membered ring in the Arbuzov reaction, thus
indicating that substitution of 1 H in the ring stabilizes it to a considerable degree, contrary to expectations. Thus,
MeOCH2CH.CH2.O.P(OEt).O and EtBr gave MeOCH2CH.CH2.O.P.(O)Et.O, b3 140-1°; use of PhCH2Br gave
MeOCH2CH.CH2.O.P(O)(CH2Ph).O, m. 88-9°; the same compd. was obtained using PhCH2Cl; this was also observed
when the MeO ester was used. PhCH2Br with EtOCH2CH.CH2.O.P(OEt).O gave EtOCH2CH.CH2.O.P(O)(CH2Ph).O, b2
198-9°; similar reaction of PhCH2Br with ClCH2CH.CH2.O.P(OBu).O gave ClCH2CH.CH2.O.P(O)(CH2Ph).O, m. 94-5°.
The action of H2O on the cyclic esters was studied. While (MeO)3P reacts vigorously with H2O, especially in the
presence of H ions, (EtO)3P can be heated with pure H2O to 100° for an appreciable time without noticeable change.
However, all cyclic esters with a 5-membered ring react vigorously with water with evolution of much heat, the reaction
proceeding either with or without ring opening. The Et ester of the cyclic ethylene glycol phosphite suffers ring opening
with H2O and gives EtO(HOCH2CH2O)PHO, b11 142-3°, n20 D 1.4825. The Me, Et, and Bu esters of cyclic
methoxypropylene phosphite give with H2O a compd. with preserved ring system: MeOCH2CH.CH2.O.P(O)H.O, b10 156-
8°, n20 D 1.4719; the same was observed with the Ph ester. Ring preservation was also observed in the action of H2O on
ClCH2CH.CH2.O.P(OBu).O, which gave ClCH2CH.CH2.O.P(O)H.O, b2 144-5°, 1.4898, and on
EtOCH2CH.CH2.O.P(OEt).O, which gave EtOCH2CH.CH2.O.P(O)H.O, b2.5 127-9°, n20 D 1.4588. All of the hydrolysis
products are colorless, viscous liquids. Attempts to prep. their metallic derivs. have been unsuccessful. Reaction of the
Me and Et 6-membered ring esters with Ph3CBr in boiling C6H6 for 0.5 hr. gave the same compd.:
MeCH.CH2.CH2.O.P(O)(CPh3).O, m. 192-3°, in which the ring remained intact. The 7-membered ring phosphites were
prepd. from MeOPCl2 or BuOPCl2 and (CH2CH2OH)2; they were just as unstable as the cyclic chlorophosphite and
deposited solid matter in a short time; no derivs. of them could be prepd. A neutral phosphite ester with an 8-membered
ring could not be prepd. Reaction of AcBr on methyl methoxypropylene phosphite was very vigorous and proceeded
without ring opening; the Ac deriv., b2 141-2.5°; similar reaction with the Et ester produced ring opening and gave a
compd., b2 131-2°, which contained 1 atom Br. The action of EtOCOCl on Et methoxypropylene phosphite also led to
ring opening and gave a compd. b1.5 144.5-46°, n20 D 1.4520. Heating CCl4 with Et methoxypropylene phosphite 24 hrs.
to 160-70° in a sealed tube gave a viscous liquid, b1.5 144-50°, which crystd. during distn. Analysis of the product
indicated that the ring was preserved and that the reaction proceeded with elimination of EtCl; however, several attempts
to reproduce the expt. failed, due to decompn. on attempted distn. The formulas for the various products given above
are probable, but have not been rigorously proved.
~3 Citings
142. Alkylene trithiocarbonates and attempted syntheses of 2,3-dimercaptopropanol (BAL)

SciFinder® Page 78
By Culvenor, C. C. J.; Davies, W.
From Australian Journal of Scientific Research, Series A: Physical Sciences (1948), 1, 236-40. Language:
The prepn. of trithiocarbonates by the action of K xanthate on the corresponding ethylene oxides, sulfides, or
chlorohydrins (cf. C., et al. (C.A. 41, 1608b)) has been extended to the following trithiocarbonates: propylene, from
propylene oxide in 70% yield, b0.2 136°; isobutylene, b24 162-70°; β-p-tolylsulfonylpropylene, m. 128°, from p-
MeC6H4SO2 CH2CH(OH)CH2Cl refluxed with KOH, and CS2 in EtOH. Propylene and 1,2-cyclohexylene
trithiocarbonates may be converted by alc. alkali to the corresponding dimercaptans [cf. Frassetti, Ber. 38, 491(1905)],
the latter in low yield. 1,2-Cyclohexylenedithiole, b15 97°, gives with BzH and HCl, crystals of 2-phenylhexahydro-1,3-
benzodithiole, m. 115.5°; with piperonal it gives the 2-(3,4-methylenedioxyphenyl) deriv., m. 125°. In an attempt to
synthesize HSCH2CH(SH)CH2OH (I) via 3-hydroxypropylene trithiocarbonate (I), glycidol was treated with K xanthate,
but only polymeric products were obtained; glycerol monochlorhydrin or monomeric hydroxypropylene sulfide (from
chloropropylene sulfide and Na2CO3 in aq. EtOH, b20 90°) gave similar results. Glycidol acetate, by ketene acetylation of
glycidol in 90% yield, is hydrolyzed by water with extreme ease, and so cannot be used for the prepn. of I.
~1 Citing
143. Alginic acid acetate

By Wassermann, Albert
DOI:10.1039/jr9480000197
Alginic acid (I) reacts at room temp. with ketene to form an ester acid (II), practically insol. in H2O and many org.
solvents, which can be converted into the Na (III) or Ca salt (IV) by treatment with an equiv. quantity of NaOH or
Ca(OH)2. III and IV can be prepd. also by treatment of the Na or Ca salt of I with ketene. Dried II, treated with NaOH,
gives III as a nontransparent gel, which binds about 800 mols. H2O/g.-equiv. Similar gels can be prepd. from II and
KOH, NH4OH, Me3N, or guanidinium carbonate. III, formed from II at 60°, is a transparent jelly which contains about
2500 mols. H2O/g.-equiv.; a similar jelly results by dispersing the moderately swollen form of III in glycerol or N(CH2-
CH2OH)3 and adding H2O. A rapid deswelling of the jelly is brought about by conversion into II or IV. If the glycerol
dispersion of III is mixed with 0.1 M solns. contg. Ca, Mg, Cu, or ferric ions, H2O-insol. ppts. result. Analyses of II-IV
show that approx. 1 Ac group has been introduced into each repeating unit of I. The rate of alk. hydrolysis of III is very
rapid at room temp. but the acid hydrolysis is slow. From viscosity data it is concluded that, during the acetylation of IV,
no detectable breakdown of the chain polymer appears to occur but during the reaction with II and III some degradation
takes place; the viscosity of solns. contg. the "recovered" III is in all cases far higher, however, than that of solns. of low
mol. uronic acids.
~2 Citings
144. Acetic esters of aliphatic polyalcohols

By Bertolina, Giacomo
From No Corporate Source data available (1948), IT 431390 19480227, Language: Unavailable, Database: CAPLUS
Polyalcs. are allowed to react with Ac2O as in Ger. 347,897 of Dec. 16, 1919. The AcOH which is formed is distd. off
from the reaction product until its concn. is reduced to 2%, then concd. NaOH is added to neutralize it and to form an
AcONa ppt. which also removes the H2O of the mixt. as water of crystn. In the reaction between glycerol and Ac2O the
yield of triacetin (purity 99%) was over 95%.
~0 Citings
145. Hydrogenolysis of carbohydrates. III. The formation of a DL-lactone and abnormal reaction product
By Jyodai, Sakae
From Nippon Kagaku Kaishi (1921-47) (1949), 52(Ind. Chem. Sect.), 248-9. Language: Unavailable, Database:
CAPLUS
The DL-lactone, apparently erythronic acid lactone (I), in the glycerol fraction is suggested as being a by-product formed
in the hydrogenolysis of carbohydrates. It is difficult to sep. I from glycerol but, when isolated, it shows the following
phys. properties: b10 125-35° or b760 230-50°, d20 4 1.03, n20 D 1.44. Analytical data obtained for the Ba salts of the
acetylated and methylated products of I show fairly good agreement with the values calcd. for the resp. derivs. No
detailed studies are made on the abnormal reaction products, except that the product is fractionated and the d. and n of
each fraction are detd.
SciFinder® Page 79
~1 Citing
146. Determination of glycerol in galenical preparations

By Mikkelsen, V. Helweg
From Archiv for Pharmaci og Chemi (1949), 56, 123-73. Language: Unavailable, Database: CAPLUS
cf. C.A. 43, 2895a. A detailed evaluation of various analytical procedures for the detn. of glycerol (I) with special
emphasis on the dichromate oxidation, the acetylation, sp.-gr. detn., n detn., and the colorimetric method. The
dichromate oxidation method (C.A. 42, 720c) is the best available method for the detn. of I in galenical prepns. Denigè
qual. method (C.A. 4, 561) using the blue-green color developed by the action between the oxidation product
[methylglyoxal (II)] of I, and codeine is adapted for detn. of I. The color developed has an absorption max. at 6500 A.
~0 Citings
147. Browning reaction of proteins with glucose

By Mohammad, Ali; Fraenkel-Conrat, Heinz; Olcott, Harold S.
From Archives of Biochemistry (1949), 24, 157-78. Language: Unavailable, Database: CAPLUS
The rate of browning of bovine serum albumin (I) in the presence of glucose (II) was followed by optical d. measurements
at 500 mµ. At a given temp., there was a short induction period, followed by a protracted linear increase. The log of the
rate (based on the linear portion) of reaction was a straight-line function of the reciprocal of the abs. temp. from 25-65°.
At 70° gels were obtained. The apparent activation energy was 30.3 kcal. From pH 4 to 10 the log of reaction rate rose
linearly. The rate of browning was dependent on I concn. within the range 2-6%, but not within 6-9%, and was
dependent on II concn. throughout the range studied (2-50%). Below 10% II gelation interfered with optical d.
measurements. Sucrose or glycerol, but not NaHSO3, appeared to inhibit browning. NaHSO3 (0.04 M) caused gelation
even in the presence of 15% Na salicylate and 15 or 30% urea. Cu in a concn. of 0.02% as CuSO4 accelerated the rate
of browning of I but did not appear to affect the rate of disappearance of NH2 groups. Browning rate was essentially the
same in 0.1 M phosphate, barbital, or HCO3 - buffer. Freeze-drying of the dialyzed brown product gave a red-brown
powder (III) contg. all the original N and 120-125% of the wt. of I used. III had an isoelec. point at pH 4.2 4.4. III had a
lower isoelec. point than I both because of the loss of total basic groups of the I and because of an increase in total acid
groups, presumably from the browned II fragment. Solns. of III heated for several hrs. to 100° at pH 3.5 or 7.0 showed
no signs of coagulation. At pH 3.6-3.7 and ionic strength 0.1, the electrophoretic mobilities of I and III were, resp., 4.31
and 2.53 rising, and, resp., 4.84 and 2.71 falling, in units of 10-5 sq. cm./v.-sec. at 0°. Different prepns. of III had mol.
wts. of 107,000-291,000, as detd. osmotically. Ultracentrifugation of III indicated the presence of several components. III
had an absorption band at 280 mµ and absorbed ultraviolet light less at lower than at higher pH values. An absorption
band for I was found at 400 mµ. III was digested more slowly than I by cryst. pepsin, and was digested still more slowly
after 4 hrs. heating at 100° in soln. III yielded up to 4.1% II upon acid hydrolysis, and appeared to be responsible for all
the color in reaction mixts. Denatured I appeared to react with II as did native I. Free NH2 groups decreased as the
browning of I, lysozyme, chymotrypsinogen, or synthetic polyamino compds. proceeded. Acetylated or guanidylated I,
guanidylated human serum albumin, or edestin failed to brown, even after 6 days or more at 53° in 30% II at pH 7. The
acetylated I did turn brown after 2 hrs. at 70°. Although solns. of methylguanidine sulfate in 30% II could be heated for
several hrs. at pH 7 without developing color, the apparent arginine (IV) contents of I and protamine sulfate were
decreased after reaction with II. The increase in the apparent IV content of edestin after subjection to the browning
reaction in the presence of added alanine, indicates that the guanidyl groups are involved in secondary reactions initiated
by NH2 groups. In a similar manner, amide groups were shown not to be involved. The amino acid contents of acid
hydrolyzates of I and III were detd. microbiologically. Lysine and IV contents were lower by more than 50% in III, but
other amino acids studied, except possibly histidine and tyrosine, were not affected. Chem. analysis showed the
tryptophan content of I and other proteins to decrease during browning. Guanidine failed to participate in the browning
reaction. The polyamine compds. used were prepd. by polymerizing tyrosine with HCHO, and by treating 1 g.
polyglutamic acid methyl ester (Fraenkel-Conrat, et al., C.A. 39, 3315.9) with 9 ml. hexamethylenediamine at 40° for 3
days, and then purifying by prolonged dialysis. 50 references.
~11 Citings
148. Analytical characterization of alkyd resins

By Hanson, N. W.
From Journal of the Oil and Colour Chemists' Association (1949), 32, 137-49. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 80
With oil-free alkyd resins a detn. of nonvolatile matter is one of the first tests required, and then a dry heating test (for
glyceryl esters, phthalic alkyds, or maleic esters), and a phenolphthalein test (for combined phthalic acid), fusion with
KOH (liberation of monohydric alcs.), Liebermann-Storch test (rosin and its esters, cyclohexanone resins), and a Na
fusion test for elements if necessary. For the identification of individual acids, the prepn. of a p-nitrobenzylbromide deriv.
from the K salt is very effective, as the ester produced has a sharp m.p.; also a mixed m.p. detn. with an authentic
specimen of the ester generally removes all doubts of identity. Table I gives characteristics of the 10 most probable
dibasic acids, one of which (diglycolic acid) gives trouble but can be isolated from concd. aq. soln. of K salts by addn. of
calcd. amt. of H2SO4, followed by an excess of abs. alc. The alc. soln. of the acid is then filtered from K2SO4 and evapd.
The resulting di-p-nitrobenzyl diglycolate (apparently not previously described) m. 122° (cor.). Various methods in the
literature for detn. of maleic acid are mentioned. The polyhydric alcs. produced by hydrolysis of alkyd resins are present
in the alc. KOH filtrate after removal of K salts of dibasic acids. For the detn. of polyhydric alcs. periodic acid oxidation
methods are used and for detection, the extd. alcs. are converted to a suitable deriv. (acetate, benzoate, or 3,5-
dinitrobenzoate) which are listed in Table II. The benzoate is prepd. by the usual Schotten-Baumann method. Oil-
modified alkyd resins are often considerably more complex as they may also contain various natural and synthetic resins;
a method is given for the commonly occurring types. Preliminary tests on the nonvolatile matter should be made as with
oil-free alkyds: dry heating, KOH fusion, and Liebermann-Storch. Then tests are applied for unsapond. matter, fatty and
resin acids are recovered and identified. Tung, oiticica, dehydrated castor, linseed, and perilla oils can be identified by
this means. Other characterization tests applied are for acid value (formation of half-esters from dibasic acid anhydrides
and alcs.) and the hydroxyl value (by acetylation with excess Ac2O in C5H5N, excess Ac2O detd. by titration). It is also
possible closely to est. for practical purposes the "oil-length."
~0 Citings
149. A glycolipide produced by Pseudomonas aeruginosa

By Jarvis, F. G.; Johnson, M. J.
DOI:10.1021/ja01180a073
A cryst., acidic glycolipide (I) was produced by 3 strains of P. aeruginosa on peptone-glycerol broth. I could not be
isolated in cryst. form when the peptone was replaced by tryptone or the glycerol by glucose. Cryst. I was obtained by
adjusting the pH of the culture to 2 with H2SO4 and refrigerating 2-3 days. I is sol. in ether, EtOH, Me2CO, dioxane, and
dil. NaHCO3; m. 86° [α]D -84° (c 3, CHCl3), mol. wt. about 650. Quant. acetylation showed 4.3 OH groups per mol. I
gives a pos. Molisch and neg. Fehling test. I loses 1 mol. of water when heated at 60° for 24 hrs. On acid hydrolysis I
yields 2 mols. of a sugar identified as L-rhamnose and 2 mols. of an acid, [α]D -21°, m. 47-8°, S-benzylthiuronium salt m.
129-30°. Oxidation with chromic acid produced caprylic acid; amide m. 105-6°. It is concluded tentatively that the acid is
1-β-hydroxydecanoic acid. The following tentative formula is proposed:
~129 Citings
150. The significance of growth factors in the metabolism of lactic acid bacteria
By Moller, Ernst-F.
From Milchwissenschaft (1950), 5, 313-16,359-62. Language: Unavailable, Database: CAPLUS
A discussion on the importance of lactic acid bacteria in reactions involving: (1) vitamin B1 and pyruvic acid; (2) vitamin
B2, nicotinic acid, adenine, and lactic acid; (3) phosphorylations and adenine; (4) conversion of galactose into glucose
and uracil; (5) vitamin B6 and transamination, racemization and amino acid decarboxylation; (6) pantothenic acid and
acetylation in citric acid synthesis; (7) biotin and the Wood-Werkman reaction, and oleic acid synthesis; (8) folic acid and
the synthesis of purines, pyrimidines, and certain amino acids; (9) vitamin B12 and purine and pyrimidine synthesis.
~0 Citings
151. Rapid determination of glycerol in commercial glycerol

By Giacomelli, Piero
From Industria della Vernice (1950), 4, 11. Language: Unavailable, Database: CAPLUS
A method involving acetylation with acetic anhydridepyridine and back-titration is described.
~0 Citings
SciFinder® Page 81
152. Molecular structure and solubility of polyvinyl acetate, polyvinyl alcohol, and re-acetylated polyvinyl
alcohol
By Dupre, A.
From Plastica (1950), 3, 17-25. Language: Unavailable, Database: CAPLUS
The disagreement of previous investigators (C.A. 30, 8430.8; 37, 6244.7) on the chain cleavage during hydrolysis of
polyvinyl acetate (I) is due to the fact that polyvinyl alc. (II) in water does not form a true soln.; this was proven by
ultramicroscope and electron microscope photographs, which show particles of 0.05-2 µ diam. Contrary to theory, the
intrinsic viscosity of II in water decreases with increasing temp. It was shown by hydrolysis of I and acetylation of the
resulting II that chain cleavage took place during hydrolysis; cleavage was greater when the mol. wt. was greater. Addnl.
cycles of hydrolysis and acetylation produced no further changes. Better solvents give solns. of higher intrinsic viscosity.
Data on the viscosity of H in glycerol-H2O (III) and HCONMe2-H2O (IV) are given; IV is a better solvent than III; III is
better than H2O.
~0 Citings
153. Molecular structure and solubility of polyvinyl acetate, polyvinyl alcohol, and re-acetylated polyvinyl
alcohol
By Dupre, A.
From British Plastics and Moulded Products Trader (1950), 22(No. 249), 89a-98. Language: Unavailable, Database:
CAPLUS
The disagreement of previous investigators (C.A. 30, 8430.8; 37, 6244.7) on the chain cleavage during hydrolysis of
polyvinyl acetate (I) is due to the fact that polyvinyl alc. (II) in water does not form a true soln.; this was proven by
ultramicroscope and electron microscope photographs, which show particles of 0.05-2 µ diam. Contrary to theory, the
intrinsic viscosity of II in water decreases with increasing temp. It was shown by hydrolysis of I and acetylation of the
resulting II that chain cleavage took place during hydrolysis; cleavage was greater when the mol. wt. was greater. Addnl.
cycles of hydrolysis and acetylation produced no further changes. Better solvents give solns. of higher intrinsic viscosity.
Data on the viscosity of H in glycerol-H2O (III) and HCONMe2-H2O (IV) are given; IV is a better solvent than III; III is
better than H2O.
~0 Citings
154. Actinomycete pigments. I. Actinorhodin, a red antibiotically active pigment from actinomycetes
By Brockmann, Hans; Pini, Henning; Plotho, Olga v.
From Chemische Berichte (1950), 83, 161-7. Language: Unavailable, Database: CAPLUS
SciFinder® Page 82
The formation of pigments by some actinomycetes (I) can be used for their classification, although it depends to a large
extent on the type of medium used in their culture. Only the yellow actinomycin A (II) and the red litmocidin have been
obtained so far in a cryst. state (cf. Waksman and Tishler, C.A. 36, 2883.8; Gause and Brashnikowa, C.A. 39, 1893.3).
The pigment-producing I are divided into the following groups: (a) strains with a dark-red micelle which colors peptone-
agar nutrient deep blue; (b) strains which color the nutrient yellow in a way similar to II and which are tentatively
designated actinomycin C; (c) strains producing yellow pigments which are sol. in CHCl3 and dissolve in aq. alkali with an
orange or violet color; (d) strains which produce red H2O-sol. or -insol. pigments which dissolve in alkali with a violet
color; (e) strains which form brown humin-like products; and (f) strains with a light-red micelle the pigment of which is not
sol. in the nutrient. Group a comprise the most significant pigment producers. They have been isolated from the soil of
forests near Göttingen. The deep-blue color which they produce in peptone-agar is caused by a red pigment called
actinorhodin (III), insol. in an aq. acid medium but sol. in aq. alkali with a bright-blue color. A nutrient composed of 2%
glycerol, 0.25% glycocoll, 0.1% K2HPO4, 0.2% NaCl, 0.005% MgSO4, 0.001% FeSO4, and 0.001% CaCO3 in an infusion
of corn or wheat bran (pH 6.5-6.8) is inoculated in 1.5-l. batches with an actinomyces strain No. 100 and incubated 25-30
days at 30°, after which the culture is a brown-red color. With invert sugar as C source the color fails to appear. At pH 6
the growth and the pigment production are small; at pH 7.5 the growth is good and the pigment goes into soln. with a
violet color; at a higher pH the soln. is colored deep blue but the isolation of the pigment is difficult. At 20° the growth of
the micelle is considerably slowed down. From 27-l. incubated culture soln., 44 g. dried micelle is obtained, contg. 15%
pigment as detd. colorimetrically. The finely powd. violet material is extd. in the cold with EtOH-ether (1:1) and CHCl3,
thus removing fats, lipoids, and a prodigiosin-like pigment and leaving 27% micelle with 24% pigment content. The
micelle powder is extd. 0.5 hr. with cold 0.5 N NaOH, and the filtered dark green soln., which turns blue on exposure to
the air, is acidified with dil. HCl, causing the red pigment to sep. It is filtered, dried, powd., and extd. in a Soxhlet with
dioxane. Concn. of the dark-red soln. and recrystn. of the product give 4.2 g. III, C24H22O11, fine bright-red needles from
anisole, dioxane, or tetrahydrofuran, decompg. at 270° without melting. Its soln. in dioxane is red, λmax. 560, 523 mµ; in
concd. H2SO4 + B2O3, violet, λmax. 581, 532 mµ; in concd. H2SO4, blue, λmax. 621, 573 mµ; in NaOH, blue, λmax. 641,588
mµ; in Ac2O, red, λmax. 560, 520 mµ; in Ac2O + pyroboroacetate (IV), when cold, violet-blue, λmax. 589, 541 mµ; in warm
IV, violet-blue, λmax. 584, 543 mµ. Attempts to obtain any identifiable products from III on Zn dust distn. at atm. pressure
or in a high vacuum, or by reduction with HI failed. On catalytic hydrogenation of 540 mg. III in 100 cc. dioxane in the
presence of 65 mg. PtO2 1 mol. H is absorbed very quickly and another within 24 hrs. From the yellow, light-blue
fluorescent, soln. which, in contact with air, turns red again, 150 mg. hydrogenated product is obtained as red needles
and is still under investigation. Warming 200 mg. III in 30 cc. Ac2O contg. 1 drop concd. H2SO4 gives a tri-Ac deriv.,
clusters of pale yellow needles from dil. AcOH, decompg. at 260° without melting. III does not contain MeO or HOCH2
groups. On oxidation of III according to Kuhn and Roth, it gives AcOH in an amt. corresponding to 2 MeC- groups. A
Zerewitinoff detn. shows the presence of 5 active H atoms. Of the 3 OH groups at least 2 are phenolic and are in α-
position in a quinone system. On reductive acetylation no cryst. product is obtained. III is methylated by CH2N2 in ether,
giving a mixt. of methylated compds. sol. in alkali with a blue color but insol. in NaHCO3, whereas III dissolves in
NaHCO3 with a blue-violet color. It has not yet been sepd. III is antibiotic in a diln. of 1:100,000 in buffered soln. towards
Staphylococcus aureus.
~13 Citings
155. γ-Substitution in the resorcinol nucleus. VII. Fries and Friedel-Crafts reaction of o- and p-orsellinic esters
By Saraiya, P. R.; Shah, R. C.
From Proceedings - Indian Academy of Sciences, Section A (1950), 31, 213-23. Language: Unavailable, Database:
CAPLUS
SciFinder® Page 83
cf. C.A. 43, 7925a. o-Orsellinic esters exhibit γ-reactivity, such as in a Friedel-Crafts acetylation, while with p-orsellinic
esters, where the γ-position is occupied, substitution occurs in a β-position. In a Pechmann condensation, e.g., 2 g. Me
o-orsellinate (I), m. 138°, and 2.4 cc. AcCH2CO2Et, cooled in ice, are treated with 4.0 cc. concd. H2SO4, allowed to stand
overnight, and dild. with ice water, to give 45% Me 5-hydroxy-4,7-dimethylcoumarin-6-carboxylate (II), m. 195-6°. II (1 g.)
kept with 10 cc. 5% KOH 30 hrs. at room temp. and neutralized with 1:1 HCl gives the free acid (III), m. 248°. III (0.25 g.)
in quinoline heated 1 hr. at 170° with Cu bronze, treated with excess Et2O, filtered, the Et2O evapd., and the residue
treated with dil. HCl gives 5-hydroxy-4,7-dimethylcoumarin, m. 258°. Me 4,6-diacetoxy-2-methyl-benzoate (IV), m. 55°, is
prepd. from 10 g. I, 15 cc. Ac2O, and a few drops pyridine by the usual manner. An intimate mixt. of 0.5 g. IV and 1.2 g.
(2.2 moles) powd. AlCl3 is heated 1.5 hrs. at 100°, cooled, treated with ice and concd. HCl, extd. with Et2O, the exts.
washed with NaHCO3 soln., and while no product is obtained from the Et2O fraction, acidification of the bicarbonate soln.
and extn. with Et2O gives Me 3,5-diacetyl o-orsellinate (V), m. 100° (from MeOH), when the Et2O soln. is worked up in
the usual manner; oxime, m. 185°. Boiling V 1 hr. with N NaOH gave γ-orcacetophenone, m. 146°. When 3.3 moles
AlCl3 is used, along with a trace of V, there is also obtained a compd. identified as Me 5-acetyl-o-orsellinate (VI), m.
101°. A Friedel-Crafts reaction of 0.5 g. I, 1.1 g. (2.9 moles) AlCl3, and 0.5 cc. (1.5 moles) Ac2O in PhNO2 gives VI;
when an excess of Ac2O (2.5 moles) or 3 moles AcCl is used, mainly V, with a trace of VI, is formed. By similar reactions
Et o-orsellinate, m. 42°, yields Et 3,5-diacetyl-o-orsellinate (VII), m. 97°, in a Fries transformation; it is isolated as the
acid, m. 96°. With PhNO2 as solvent, both VII and Et 5-acetyl-o-orsellinate (VIII), m. 87°, are obtained. Friedel-Crafts
reactions yield VIII with normal quantities of reactants, but with excess Ac2O mainly VII is formed, with a trace of VIII.
Orcinol diacetate, b10 240° (6 g.), and 12 g. powd. AlCl3 heated 2 hrs. at 150°, cooled, and ice and HCl added, give 2,4-
diacetylorcinol, m. 96°. Deacetylation with either concd. H2SO4 or boiling alkali gives γ-orcacetophenone. The diacetate
of Me p-orsellinate (m. 99°), prepd. as usual, m. 70°; in a Fries reaction it yields 3-acetyl-p-orsellinic acid (IX), m. 170°
(effervescence). Decarboxylation of IX gives β-orcacetophenone (X), m. 158°. Friedel-Crafts reaction results in IX only,
and the Et ester also yields IX in a Fries reaction. X (0.5 g.), 1.0 g. KHCO3, and 1 cc. anhyd. glycerol heated in a current
of CO2 5 hrs. at 100-5°, dild. with H2O, and acidified yield IX; attempted carboxylation at 145-50° gives p-orsellinic acid.
~0 Citings
156. Trifluoroacetic acid as an esterification catalyst

By Morgan, Paul W.
DOI:10.1021/ie50503a046
cf. C.A. 45, 5619d. (CH2OH)2 (10 ml.), 40 ml. Ac2O (I), and 0.1 ml. CF3CO2H(II) gave a rapid reaction after 1 hr., the
temp. reaching 100°; after 2 hrs. 87% (CH2OAc)2 was obtained. C3F7CO2H (III) (0.2 ml.) produced a similar reaction.
Glycerol reacted with I and II, but the temp. was not allowed to rise above 45-50°; after 90 min. a nearly quant. yield of
(AcOCH(CH2OAc)2 remained after distn. of the I, II, and AcOH (IV) formed by the reaction. Without temp. control the
temp. rose to 100°; III had the same effect, as did (CF3CO)2O. AmOH, I, and II gave a nearly quant. yield of AcOAm;
refluxing AmOH, II, and IV gave 43% ester, rising to 69% if the H2O formed was removed during the reaction by
azeotropic distn. Cellulose acetate was heated with I, II, and IV 3 hrs. at 110° and the soln. treated with 75% aqueous IV
and heated 3 hrs. at 80°; the product, sol. in Me2CO, contained 2.61 Ac groups/anhydroglucose unit; the viscosity of the
product was practically unchanged after 4 years. Hydroxyethylcellulose (V), contg. 0.3 mol. HOCH2CH2 group/glucose
unit, was heated with I, II, and IV 90 min. at 80°, and the soln. treated with 50% aq. IV and heated 3 hrs. more at 80°; the
product contained 2.39 Ac groups/glucose unit, and formed heat-stable films. The speed of the reaction increased with
increasing amt. of II. V with II, EtCO2H, and (EtCO)2O, gave a product contg. 2.72 EtCO groups/anhydroglucose unit. III
was as good a catalyst as II in the acetylation of V; CCl3CO2H was less effective.
~1 Citing
157. The oxidation of di-tert-butylpyrogallol by oxygen in alkaline solution

By Campbell, Tod W.
DOI:10.1021/ja01153a044
SciFinder® Page 84
cf. C.A. 45, 9368c. The autoxidn. of di- tert-butylpyrogallol (I) in alk. media with air gives an o-quinone (II), which is
partially cleaved to 2-hydroxy-3,5-di-tert-butylmuconic acid (III), and partially rearranged and oxidized to 2,4-di-tert-butyl-
1,3-cyclopentanedione (IV) and 2,4-di-tert-butyl-1,3,5-cyclopentanetrione (V). Pyrogallol (252 g.), 250 cc. Me3CCl, 0.05
g. FeCl3, and 500 cc. AcOH refluxed 3 h. (250 cc. Me3CCl added after 1 h.), the soln. concd. to 400 cc. in vacuo, water
added to the cooled soln. to turbidity, and the soln. seeded, dild. to 3 l., let stand overnight, and filtered yielded 100 g. I,
m. 120° (from dil. AcOH). I forms Me esters with CH2N2 and Me2SO4. I (90 g.) in 4 l. MeOH contg. 200 cc. 7 N NaOH
aerated until colorless, the soln. dild. to 10 l. with water, acidified with H2SO4, extd. with 3 l. Et2O, the ext. concd. to 500
cc., extd. with aq. KHCO3, and the aq. layer acidified yielded 41 g. white, cryst. powder, a mixt. of III and 3,5-di-tert-butyl-
2-pyrone-6-carboxylic acid (IIIA). The Et2O on evapn. yielded 39 g. of a mixt. of the compds. (VI) (55%) and (VII) (45%).
The mixt. dissolved in 150 cc. isoöctane, the soln. chilled in ice, and filtered yielded 6.5 g. VI (from isooctane); the
mother liquor chilled in Me2CO-Dry Ice, filtered rapidly, the cryst. material sublimed at 110° and atm. pressure, and the
needles selected from the sublimate manually and recrystd. from aq. MeOH yielded pure VII; or (better method) 15 g.
crude VII (contg. 10-20% VI) was heated 30 min. at 150° with 7 g. KOH in 50 cc. glycerol, the soln. poured into water,
acidified, VII and a product from VI taken up in Et2O, and the product extd. with KHCO3, yielding pure VII. VI m. 122.5-
23°, VII m. 108-8.5°. III with Ac2O, AcCl, and HBr in AcOH, yielded IIIA, m. 203-5° (sealed tube) (sublimed at about
200°). IIIA (1 g.) refluxed 15 min. in 15 cc. N KOH and the soln. acidified yielded III. IIIA (33 g.) heated 30 min. at its b.p.
was decarboxylated to 3,5-di-tert-butylcoumalin (VIII), thick needles with a pleasant, camphoraceous odor from
isoöctane, b25 152°, m. 67.5-68°. VIII (100 mg.) heated overnight at 150° in 10% KOH was apparently hydrolyzed. No
oxime could be prepd. VIII was not changed by refluxing 36 h. with amalgamated Zn and HCl. VIII (0.1746 g.) and 0.235
g. Pt oxide absorbed 4 mol H at 26° and 757 mm. VI (100 mg.) in 2 cc. MeOH treated with excess Me2SO4 and alkali
gave a good yield of the Me ether(IX, R = Me), needles, m. 101.5-103°; also obtained from VI and CH2N2. VI (300 mg.)
and 1 cc. each of pyridine and Ac2O let stand overnight and poured into water yielded the acetate (IX, R = Ac), large
cubes from isoöctane. VI (200 mg.) and 0.5 cc. PhNH2 heated 1 h. at 100° gave unchanged VI. VI with Br or Cl in AcOH
yielded orange-colored oils. VII on acetylation yielded a noncryst. enol acetate (presumably). VII (1.2 g.) with excess
30% Br in AcOH yielded the compd. (X): a stable form, long, bright-orange spears, m. 110-11.5°, and a metastable form,
garnet-colored prisms. The 2 forms probably are cis-trans isomers. X (orange form) reverts to VII with Zn in AcOH or
with H and Pt. X in PrOH with N2H4.H2O gave N and the compd. (XI). Chlorination of VII yielded an orange, cryst.
compd., m. 82-3°. VII (0.4618 mmole) in 20 cc. AcOH treated with 1 cc. bromide-bromate (1 equiv. of Br), the soln. dild.
with water, and the soln. extd. with Et2O yielded XI, feathery leaflets from dil. AcOH, m. 131-1.2°. XI with alkali yields the
compd. (XII), m. 154.5-55°. X and o-(H2N)2C6H4 yielded XI. VI with Br in glacial AcOH gave oily orange substitution
products which were not identified but presumably have the structure (XIII). XI or XIII with Zn and AcOH yielded VII.
~2 Citings
158. The effect of acetyl donors on creatine formation in rats and dogs
By Kandel, Alexander; Chenoweth, Maynard B.
cf. C.A. 44, 3145h. Glycerol monoacetate is more effective than NaOAc in providing Ac groups for the synthesis of
creatine in the intact dog and in kidney cortex slices and homogenates of the rat. Glycerol is ineffective in this respect in
dogs. Guanidine depresses the methylating activity of the liver (as evidenced by creatine synthesis) to a greater extent
than it does the acetylating activity of the kidney cortex of the rat. The effect of guanidine administration in the dog may
be based on the type of activity of guanidine on the rat kidney cortex and liver in vitro.
~0 Citings
159. Preparation of ethyl DL-glycerate-1-C14 and glycerol-1-C14

By Doerschuk, Albert P.
DOI:10.1021/ja01146a096
Complete details are given of the prepn. of Et DL-glycerate-1-C14 and glycerol-1-C14 by the addn. of HC14N to
HOCH2CHO, followed by hydrolysis, esterification, acetylation, and reduction. The glycerol had a sp. activity of 1.77 ×
105 counts/min./mg., which corresponds to an incorporation of 63.4% of the initial radioactivity.
~0 Citings
160. Esters of hydroxy fatty acids

By Forsman, W. R.
From No Corporate Source data available (1951), SE 132999 19510925, Language: Unavailable, Database: CAPLUS
SciFinder® Page 85
An unsatd. fatty acid or ester is treated with H2SO4 and the sulfated HO fatty acid or ester formed is sepd., esterified with
an alc. in the presence of a mineral acid, and the resulting mixt. of alkylated HO fatty acid and its sulfate sepd. Examples
are given of the prepn. of an ester starting from oleic acid and EtOH. The use of linoleic acid and the acids from tall oil
and of MeOH and iso-PrOH also is referred to. The HO fatty acid ester may be subjected to alcoholysis with another
alc., e.g., glycerol, or the HO group may be acetylated.
~0 Citings
161. Antibiotics from actinomycetes. V. Actinomycin C

By Brockmann, Hans; Grubhofer, Nikolaus; Kass, Wilhelm; Kalbe, Hans
From Chemische Berichte (1951), 84, 260-84. Language: Unavailable, Database: CAPLUS,
DOI:10.1002/cber.19510840305
SciFinder® Page 86
cf. C.A. 44, 6914c; 45, 5230h. A new antibiotic, actinomycin C (I), has been isolated from Streptomyces chrysomallus (II)
and is investigated chemically. II is grown at 28° on a nutrient contg., per 1., 20 g. glycerol, 10 g. KNO3, 5 g. K2HPO4, 5
g. NaCl, 5 g. MgSO4.7H2O, and 0.01 g. FeSO4.7H2O. After 26 days the mycelium is filtered, dried at 100°, powd., and
extd. with C6H6. The residual aq. soln. is exhaustively extd. with BuOAc, the ext. evapd., and the residue combined with
the C6H6 ext. and filtered through an Al2O3 II column. Upon development of the chromatogram with C6H6 an orange-red
zone, contg. I, is obtained and eluted with EtOAc. The eluate is concd. in vacuo and the residue dild. with twice its vol.
CS2, causing I to crystallize. It is washed with EtOAc-CS2 (1:2) and recrystd. from EtOAc, giving hexagonal alizarin red
bipyramids, m. 252° (decompn.). Because the compn. of I seems to change with the age of the strain, I obtained in the
early expts. is designated "old" (Ia), that obtained later, "new" (Ib). Ia, C62H89O17N11, contains 59.05% C, 7.07% H,
12.24% N, 5.4% N-Me, 0.63% active H; d. 1.0155, [α]17 D -319° ± 3°, -312°, -290°, -250°, -240° (c 5, 2.5, 1, 0.5, 0.25,
EtOH); soly. in abs. EtOH is 7%, in C6H6, 27%, in CHCl3 65%, Me2CO 120%, H2O 0.14%; mol. wt. 705 (Rast), 915
(Beckmann, PhOH), 876-944 (Barger-Rast, tetrahydrofuran). Ib, C60H83O16N11, contains 59.65% C, 6.87% H, 12.75%
N; [α]17 D -309° ± 3° (c 2.5, EtOH). I arrests the growth of Staphylococcus aureus in dilns. of up to 1:10,000,000 and
Escherichia coli in dilns. of up to 1:10,000. I is toxic to a mouse in doses of 50 mg./kg. when administered orally as aq.
soln. and 5 mg./kg. on intraperitoneal administration, within 24 hrs. I seems to be different from actinomycin A
(Waksman and Tischler, C.A. 36, 2883.8) and B (Dalgliesh, et al., C.A. 45, 6160h). On catalytic hydrogenation in AcOH
in the presence of PtO2 100 mg. Ia absorbs 1.8 cc. H and 330.9 mg. Ib 6.1 cc. H, from which mol. wts. of 1280 and 1218
are calcd. On dissolving the light-yellow hydrogenation product (III) of Ib in C6H6 the soln. changes to red-yellow by
autoxidation, giving 92% Ib. Ia (175 mg.) in BuOH and 50% HClO4, gives 180 mg. C62H89O17N11.3HClO4, m. 192° (cor.).
Ia refluxed 2 hrs. with Ac2O and C5H5N is recovered unchanged. Reductive acetylation of 200 mg. Ia in 2 cc. Ac2O and
1 drop C5H5N with 500 mg. Zn dust gives 140 mg. leucoacetate, C62H89O17N11Ac2, light-yellow rectangular platelets, m.
253° (cor.). I does not seem to contain primary or secondary NH2 groups and gives a neg. ninhydrin reaction. With
Nessler's reagent I gives a gray-brown ppt. which can be used for the marking of I on the paper chromatogram. Because
of indications that I may be a mixt. of closely related compds. Ib is subjected to a 40-step countercurrent distribution (C.A.
44, 7096e), by using the solvent pairs BuOH-AcOH, C6H6-AcOH, and HCO2H-CH2Cl2 and thus producing a distribution
curve which indicates that Ib is a pure compd. Although Ib is sol. in ether-HCl only to 0.1% in each phase, 80 mg. is
fractionated in an app. that holds 800 cc./step. Fractions 19-25 are redistributed in a 100-cc./step app., giving a curve
that indicates a mixt. However, since I is sensitive towards acids it is possible that in ether-HCl some hydrolysis products
are formed although I is not changed in 6% HCl during 2 hrs., the time required for the distribution process. The fact that
threonine-free fractions are obtained can be explained only by the assumption that I is a mixt. From a comparison of the
curves obtained from various prepns. of I produced by the original strain and by strains repeatedly transferred, it is found
that the latter produce more complicated mixts. than the former. For the elucidation of the amino acid portion of I,
uniform samples must be used, for that of the chromophoric part, a mixt. can be used. On hydrolysis of I with HCl a
black-brown ppt. is obtained which originates from the amino acid-free portion and contains some black melanin-like
products from which no cryst. compd. can be isolated. Ia (487 mg.) is heated with 3 cc. concd. HCl 9 hrs. in a sealed
tube at 125° and the tube is opened in such a way that the gases are passed through B(aOH)2, giving 51.8 mg. BaCO3
(0.75 mol./ mol. I). The black ppt. amounts to 103 mg. (24%). The acid soln. is decolorized and evapd., giving 69%
residue (IV) with 3.3% NH2-N and [α]16 D -47.8°. IV contains 2.06 mg. NH3-N, detd. with H2PtCl6. Refluxing 36 hrs. 6.18
g. Ia in 40 cc. 30% H2SO4 at 110° gives 0.72 mol. CO2 and 1.4 g. (23%) black ppt. contg. 54.53% C, 5.11% H, 6.22% N,
and 1% N-Me. The filtrate is freed of H2SO4 with Ba(OH)2 and evapd. to dryness, giving 3.9 g. (63%) cryst. residue (V).
V (1.93 g.) is extd. with 20 cc. EtOH, leaving 0.83 g. residue (VI). The residue (1.1 g.) of the alc. ext. is extd. twice with
10 cc. 99% EtOH and leaves 90 mg. residue (VII) which, after 2 crystns., m. 245-55° and is identified
paperchromatographically as threonine (VIII). The filtrate of VII is treated with 30 cc. satd. alc. CdCl2 soln., the ppt.
formed is freed of Cd with H2S, and the concd. filtrate treated with reinecke acid (IX), giving 257 mg. L-proline (X)
reineckate (Xa), m. 198°, from which 60 mg. X, m. 212°, [α]17 D -78° (H2O) (picrate m. 146°) is regenerated. The filtrate
of Xa is freed of IX and concd.; it shows the RF value of valine (XI) and gives a small quantity of needles, m. 160°, which
give a red ninhydrin reaction and an intense odor of NH2Me when heated with NaOCl. Recrystn. of VI and sublimation
(170°/0.01 mm.) give 533 mg. sublimate (XII), showing the RF values of isoleucine (XIII) and XI. XII is dissolved in 2 N
NaOH, treated with 3,5-(O2N)2C6H3COCl, and the mixt. adjusted to pH 4, causing the sepn. of crystals, m. 186°.
Adjusting the pH to 3 gives 80 mg. XIII 3,5-dinitrobenzoate, m. 178°, from which, on hydrolysis with HCl, 15 mg. XIII, m.
247°, [α]17 D -14.4° (H2O) is regenerated. In another expt. with 300 mg. IV, 70 mg. XIII, m. 276°, [α]17 D -15.2° (H2O) is
obtained. IV with 9.6% total N, 3.1% amino N, and 5.1% N-Me is sepd. paperchromatographically (for details see original
paper), with ο-cresol as mobile phase and a 0.4% ninhydrin soln. in BuOH as developer. The 6 zones are cut out and
eluted with H2O. Zone 1 gives 4.3% VIII, m. 240-2°, [α]20 D 7° (H2O), which, oxidized with HIO4 gives AcH. Because of
overlapping, zones 2-4, contg. sarcosine (XIV), D-XI, and D-alloisoleucine (XV), are eluted together and
rechromatographed with BuOH-20% AcOH as phase pair, giving the same sequence of zones. Zone 2 gives 1.6% XIV,
identified by RF values of pure XIV (RF in ο-cresol 0.34, in BuOH-AcOH 0.17-0.21, in PhCH2OH 0.08, in PhOH 0.73, in
sec-BuOH 0.84, in collidine 0.08). Zone 3 gives 1% D-XI, m. 296°, [α]16 D 5.8° (H2O), -24.9° (20% HCl). Zone 4 gives
24% XV, m. 284°, [α]16 D -15.6° (H2O), -31.8° (c 2.7, 20% HCl) (phenylisocyanate m. 157°; naphthylisocyanate m. 167-
8°; HCO deriv., prepd. by heating 20 mg. with 1 cc. anhyd. HCO2H, m. 125°). Decompn. of 10 mg. with ninhydrin
according to Löhr (C.A. 44, 5422h) gives an optically active 2,4-dinitrophenylhydrazone, m. 130°. Zone 5 gives 20% X,
m. 128°, [α]18 D -75.4° (H2O) (reineckate m. 199°). Zone 6 gives 42% N-methyl-L-valine (XVI), m. 290°, [α]16 D 16.5°
(H2O), 28.6° (10 Ngr; HCl). To prevent the formation of a black ppt. on hydrolysis of I, 230 mg. I is heated with 4 cc.
concd. HCl and 160 mg. SnCl2 16 hrs. at 90°, causing the formation of a red ppt. which is extd. with BuOH. The aq. soln.
is freed of Sn with H2S, evapd., and gives the same 6 amino acids in the paper chromatogram. The yellow-red BuOH
soln. is shaken with 1 cc. 0.5% H2O2, causing a deepening of the color, evapd. in vacuo, the residue dissolved in CHCl3,
filtered through a silica column, and evapd., giving a red powder from which, on hydrolysis with concd. HCl, no amino
acids are obtained (paper chromatogram). Heating 170 mg. Ib with 5 cc. AcOH, 3 cc. HI, and 0.8 g. PH4I 12 hrs., evapg.
the mixt., distributing the residue in 10 cc. H2O and 10 cc. C6H6, and filtering the dried C6H6 soln. through a silica column
give a small brown zone and an intense blue fluorescent filtrate which, evapd., gives colorless needles, m. 114-15°. On
hydrolysis with concd. HCl no amino acids are obtained. In the original aq. phase the amino acids, except VIII, are
SciFinder® Page 87
found. Heating 598 mg. Ib with 12 cc. 6 Ngr; HCl 25 min. at 100°, dilg. the mixt. to 60 cc., extg. it with ether, and evapg.
the ether leaves no residue. The aq. soln. is evapd. in vacuo, the residue dissolved in borate buffer soln. (pH 10), and
steam distd., giving 5.9 mg. NH3. When 200 mg. Ib is kept 2 weeks with 20 cc. AcOH-10% HCl (1:1) at 37° and a
sample is tested in a bidimensional paper chromatogram with PhOH-collidine as mobile phases, only weak spots of XVI
and XV can be detected. After 8 weeks the spots of the other amino acids appear. After 16 weeks the mixt. is evapd. in
a desiccator and the residue is extd. successively with CHCl3, Me2CO, and BuOH, leaving a small amt. of a black
residue. The residues of the 3 exts. are red-brown amorphous products, give an intense green color with SnCl2, and are
free of amino acids. On heating with 20% HCl 24 hrs. a black melanin-like ppt. is formed and in the filtrate all amino
acids are found in the paper chromatogram. Heating 1 g. Ia with 10 cc. 20% HCl 20 min. at 105°, dissolving the residue
of the evapd. (in vacuo) soln. in 10 cc. H2O, filtering the soln. through an Al2O3 column, and washing the column with 0.1
N HCl produces a yellow-red zone [zone base (XVII)] and a yellow filtrate. The filtrate contg. the eluate base (XVIII) is
concd. in vacuo and treated with HgCl2 and the ppt. formed is decompd. with H2S, filtered, and evapd., giving the HCl
salt of XVIII which is readily hydrolyzed, forming the free XVIII; it gives an orange-red ppt. with HAuCl4 and a yellow-
brown picrolonate. XVII is eluted with C5H5N-H2O (1:1) and forms an amorphous picrolonate. On prolonged treatment
with HCl, XVIII changes to XVII. To obtain XVIII in a better yield, I is heated with 6 N HCl 5 min. at 100°, the mixt. is
evapd. in vacuo, and the residue extd. with H2O. The unchanged I is treated again in the same way until completely
hydrolyzed. To remove XVII the aq. ext. is passed through an Al2O3 column, XVIII is extd. from the filtrate with CHCl3,
and XVIII-HCl is formed. It gives an orange-red picrate. XVII and XVIII treated with HNO2 evolve only very little N but
form red NO compds. Hydrolysis of Ib with azeotropic HCl 0.5 hr. on a water bath, evapg. the mixt. in vacuo, extg. the
residue with BuOH, passing the BuOH soln. through Al2O3, eluting XVIII with BuOH, washing the column with EtOH,
H2O, and, finally, with 0.1 N NaOH, acidifying the alk. eluate, and extg. with BuOH-CHCl3 (1:9) give XVII-HCl which is
further purified via its picrate. XVII shows an amphoteric behavior and can be esterified with MeOH-HCl. XVII and XVIII
are reduced by SnCl2, giving a deep-green intermediate (XIX), λmax. 684, 622, 568 mµ (AcOH), and a pale-yellow leuco
compd. which is oxidized by air again via XIX to the original red-yellow compd.
~3 Citings
162. Quinolyl ketones. I

By de Diesbach, Henri; Pugin, Andre; Morard, Francois; Nowaczinski, Wojceich; Dessibourg, Joseph
From Helvetica Chimica Acta (1952), 35, 2322-32. Language: French, Database: CAPLUS
SciFinder® Page 88
A no. of quinolyl ketones (I), prepd. by the Skraup synthesis from 4-aminobenzophenones, have been reduced with
Raney Ni and H at ordinary pressure and temp. to the tetrahydro derivs. (II) and with (iso-PrO)3Al to the carbinols (III),
but could not be reduced to the tetrahydro carbinols (IV.). Raney Ni reduces III to the methylene derivs. (V) instead of to
IV. Thus 6-benzoylquinoline (VI), colorless crystals, m. 60.5° (from ligroine) [VI.H2O, white plates, m. 39-40° (from
MeOH or EtOH); picrate, m. 222°; phenylhydrazone, m. 184°; syn-oxime, m. 198-205°; anti-oxime, m. 192-5°], is prepd.
by heating p-H2NC6H4Bz, PhNO2, glycerol, and concd. H2SO4 3 h. at 160°, dilg., treating with steam, acidifying,
alkalizing, taking up in Et2O, filtering, and distg. at 240°/16 mm. Similarly are prepd. the following compds. [(a) starting
amine, and (b) corresponding quinoline deriv.]: (a) 3,4-Me(H2N)C6H3Bz; (b) 6-benzoyl-8-methylquinoline. (VII), yellowish
plates, m. 199° (from AcOH) [phenylhydrazone, m. 235-7° (from C6H6)]. (a) 4-Amino-4'-chlorobenzophenone; (b) 6-(p-
chlorobenzoyl)quinoline (VIII), m. 204° (from ligroine, b. 120-80°, then from MeOH). (a) 4-Amino-2',4'-
dichlorobenzophenone, m. 130-1° (100% yield by Raney Ni hydrogenation of the 4-nitro analog in MeOH 24 h. at 100°
and 80 atm.); (b) 6-(2,4-dichlorobenzoyl)quinoline (IX), white crystals, m. 131-2°. (a) 4-Amino-2',5'-
dichlorobenzophenone, white crystals, m. 123° (from 60% alc.), from the 4-nitro analog with SnCl2 or Na2S; (b) 6-(2,5-
dichlorobenzoyl)quinoline (X), white needles, m. 134-5° (from dil. alc.) (picrate, m. 208-9°). (a) 4-Amino-3',4'-
dichlorobenzophenone, white crystals, m, 161-2° (from alc.), from the 4-nitro compd. with SnCl2; (b) 6-(3,4-
dichlorobenzoyl)quinoline (XI), m. 139-40° (from ligroine and MeOH) (picrate, m. 173-4°). (a) 4-Amino-4'-
chlorobenzophenone; (b) 6-(4-chlorobenzyl)quinoline, m. 191.5-2° (from alc.). (a) 4-Amino-2',4'-
dichlorodiphenylmethane, blue crystals, m. 102-3° (Ac deriv., m. 141-2°), from the 4-nitro compd. with SnCl2; (b) 6-(2,4-
dichlorobenzyl)quinoline (in poor yield) (picrate, m. 167-8°). (a) 4-Amino-3',4'-dichlorodiphenylmethane, an oil (Bz deriv.,
m. 106-7°), from the 4-nitro compd. and SnCl2; (b) 6-(3,4-dichlorobenzyl)quinoline (picrate, m. 164-5°). 6-Acetyl-1,2,3,4-
tetrahydroquinoline (XII), greenish plates, m. 105-7° (picrate, m. 125°; oxime, m. 144°), is prepd. by condensing 1-acetyl-
1,2,3,4-tetrahydroquinoline with ClCH2COCl at room temp., sapong. the 1-Ac group with boiling 20% HCl, and heating in
80% alc. with powd. Fe and 2N HCl; heated 5 h. at 188° in a sealed tube with Hg(OAc)2, AcOH, and H2O it gives
yellowish prisms of 6-acetylquinoline, m. 75-6° (picrate, m. 242°). A Beckmann rearrangement of XII oxime gives 6-
amino-1,2,3,4-tetrahydroquinoline, m. 95.5-6°. Na redn. of Quinaldine in AmOH gives 93% 1,2,3,4-tetrahydroquinaldine,
acetylated with Ac2O to the 1-Ac deriv., b12 153°, yellow crystals, m. 57°; which, treated with ClCH2COCl in CS2, then
slowly with AlCl3, and let stand 2 days yields 6-(chloroacetyl)-1,2,3,4-tetrahydroquinaldine-HCl, white crystals, m. 225-6°,
converted by neutralization with dil. alkali to the free quinaldine, yellow crystals, m. 121°, which is dechlorinated in 80%
HCl with Fe and 2N HCl to 6-acetyl-1,2,3,4-tetrahydroquinaldine, m. 69°. The following 1,2,3,4-tetrahydroquinolines are
prepd. in good yield by hydrogenating 5 g. of the appropriate I in 50 mL. MeOH at room temp. and pressure in the
presence of Raney Ni, warming, filtering, washing the Ni with warm MeOH, evapg. to a small vol., and recrystg.: 6-
benzoyl (XIII), yellowish crystals, m. 113° [1-ON deriv., m. 119-20°; 1-Bz deriv., m. 131° (from 50% AcOH); 1-Ac deriv.,
m. 97° (from dil. alc.)]; 6-benzoyl-8-Me, pale yellow needles, m. 118°; 6-(p-chlorobenzoyl)tetrahydroquinoline, m. 156° (1-
ON deriv., m. 173-4°; 6-Bz deriv., m. 146°); 6-(2,4-dichlorobenzoyl), m. 137° (1-ON deriv., m. 145°); 6-(2,5-
dichlorobenzoyl), m. 153°. The Meerwein-Ponndorf redn. of I to III is carried out in nearly 100% yield by adding 10 g. of
the I in 30 mL. iso-PrOH to (iso-PrO)3Al (made by refluxing 2.5 g. Al paste 10 h. with 0.125 g. HgCl2 in 50 mL. abs. iso-
PrOH), slowly distg. the Me2CO formed, alkalizing, steam-distg. the iso-PrOH, adding boiling H2O to the residue, and
crystg. from dil. alc. Thus are prepd. the following carbinols: phenyl(6-quinolyl) (XIV), m. 127-8° (picrate, m. 190°; picrate
of the acetate (ester), m. 188°); phenyl(8-methyl-6-quinolyl) (XV), m. 133° [picrate, m. 202-3°; acetate (ester), m. 100°
(from dil. alc.)]; (p-chlorophenyl)(6-quinolyl), m. 153° (picrate, m. 186°; picrate of the acetate (ester), m. 209°); (2,4-
dichlorophenyl)(6-quinolyl), m. 161° (picrate, m. 225°; acetate (ester), m. 125-6°; picrate of the acetate, m. 212°); X, (2,
5-dichlorophenyl)(6-quinolyl), m. 161° (acetate (ester), m. 174°); (3,4-dichlorophenyl)(6-quinolyl), m. 145° (picrate of the
acetate (ester), m. 189-90°). Raney Ni hydrogenation of XIV gives 6-benzylquinoline, white crystals, m. 48-9°; similarly
XV is reduced to 6-benzyl-8-methylquinoline, m. 55°. An attempted (iso-PrO)3Al redn. of XIII to the corresponding IV
gives instead a white paste, m. 120-40°, sol. in C6H6 and CHCl3, slightly sol. in alc. 2-Benzoylquinoline is reduced by
(iso-PrO)3Al in 100% yield to phenyl(2-quinolyl)carbinol (XVI), white crystals, m. 69° (from ligroine); also obtained by
Raney Ni hydrogenation at room pressure and temp. [picrate, yellow crystals, m. 138° (from alc.)], instead of to the
tetrahydro deriv. Phenyl(1,2,3,4-tetrahydro-2-quinalyl)carbinol, b0.005 140° [1-ON deriv., yellow plates, m. 103° (from dil.
alc.); N,O-di-Bz deriv., m. 161° (from ligroine)], is prepd. by reducing 2 g. 2-benzoylquinoline 1 h. in 300 g. MeOH with H
at 70° and 50 atm. in the presence of Raney Ni, filtering, washing with MeOH, evapg. to a small vol., dilg. with H2O,
adding Et2O, and vacuum-distg. the oil. 4-Benzoylquinoline is reduced by (iso-PrO)3Al to phenyl(4-quinolyl)carbinol, m.
127° (from dil. alc.) (acetate (ester), white plates, m. 100°), and by Raney Ni hydrogenation at 100° and 70 atm. to
phenyl(1,2,3,4-tetrahydro-4-quinolyl)carbinol, m. 135° (from dil. alc.), b0.001 110-15° [1-ON deriv., yellow leaves, m. 105°
(from dil. ac.); N,O-di-Bz deriv., m. 156° (from ligroine)]. 2-Methyl-4-benzoylquinoline (XVII), bright plates, m. 118° (from
ligroine), is prepd. by heating 2 g. 2-methyl-4-quinolinecarboxamide in 30 mL. POCl3 with 3 g. PCl5 (with 2 drops water
added to start the reaction) 15-20 min. at 110°, cooling with ice, neutralizing, extg. with Et2O, crystg. from ligroine the 2-
methyl-4-cyanoquinoline (XVIII), white needles, m. 106°, and adding the Grignard reagent from 12 g. PhBr and 2 g. Mg in
30 mL. Et2O to 5 g. XVIII in 50 mL. Et2O; XVII is reduced by (iso-Pr)3Al to phenyl(2-methyl-4-quinolyl)carbinol, colorless
prisms, m. 167° (from dil. alc.) [acetate (ester), m. 103° (from dil. alc.)], and by Raney Ni hydrogenation at 100° and 70
atm. to phenyl(2-methyl-1,2,3,4-tetrahydro-4-quinolyl)carbinol, m. 162° (from dil. alc.), b0.001 130° [N,O-Bz deriv., m. 149°
(from ligroine)]. Raney Ni redn. at room pressure and temp. of 8-benzoylquinoline gives at once phenyl(1,2 3,4-
tetrahydro-8-quinolyl)carbinol, oil, b0.001 120° [1-ON deriv., yellow prisms, m. 146° (from alc.), (di-Bz deriv., m. 132° (from
ligroine)]. Nitration of 6 g. VI in 25 mL. concd. H2SO4 with 1 mL. nitrating mixt. (= 0.255 g. HNO3) added at -10°, followed
by cooling with ice, filtering, neutralizing with NH4OH, and crystg. in alc., gives 6-(m-nitrobenzoyl)quinoline, yellow
needles, m. 160°, which reduced by SnCl2 in alc. to the amino compd., yellow crystals, m. 142° (from H2O). Similarly, VII
is nitrated to 6-(m-nitrobenzoyl)-8-methylquinoline, m. 156°, which is reduced to the 3-amino compd., yellow crystals, m.
187° (from ligroine). The (dichlorobenzoyl)quinolines cannot be nitrated.
~0 Citings
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163. Proof of the structure of sedoheptulosan as 2,7-anhydro-β-D-altroheptulose

By Pratt, James W.; Richtmyer, Nelson K.; Hudson, C. S.
DOI:10.1021/ja01129a016
cf. preceding abstr. Oxidation of sedoheptulosan (I) with Na meta-periodate, hydrogenation of the resulting dialdehyde
(IA), and subsequent hydrolysis of the product yielded glycerol. Oxidation of tetramethylsedoheptulosan (II) with HNO3
yielded the optically active N,N'-dimethyl-D-arabo-2,3,4-trimethoxyglutaramide (III) and not the inactive ribo compd.
reported by Hibbert and Anderson (C.A. 25, 498). The reasons for the discrepancy are discussed. Thus I is formulated
with only a normal pyranose ring and as either 1,2- or 2,7-anhydride. Four arguments are advanced, all of which lead to
the conclusion that I is 2,7-anhydro-β-D-altroheptulopyranose. I from Sedum spectabile m. 155-6°, [α]20 D -146° (c 2,
water). Powd. I on exposure to air formed the monohydrate. Sedoheptulose sirups equilibrated with H2SO4, neutralized,
deionized, and concd. in vacuo formed crystals during the evapn., which were isolated and shown to be the hydrate, m.
101-2° after sintering at 91°, [α]20 D -134° (c 2, water) (Wolfrom, et al., cf. following abstr.) IA, [α]20 D -16.9°, from 6.30 g. I
on treatment with HOBr yielded C6H6CaO7.3H2O (IV), [α]20 D 41.8° (c 1, water). IV (2 g.), 1.7 g. ο-(H2N)2C6H4, 2.5 cc.
HCl, 4 cc. water, and 0.5 cc. EtOH heated 3 hrs. in an oil bath at 135 ± 5°, dild. with 10 cc. water, heated with C, filtered,
and the soln. made strongly alk. with NH4OH yielded 0.75 g. 4-D-glycero-2-hydroxymethyl-2,4-cis-di(2-benzimidazolyl)-
1,3-dioxolane (V), m. 137° (when anhyd.) to a sirup which liquefied at about 160°, [α]20 D -12.9 ± 1.5° (c 1.6, N HCl). I
(50 g.) oxidized to IA with an excess of paraperiodic acid, the soln. made barely alk. to phenolphthalein with Ba(OH)2,
filtered, balanced with H2SO4, concd. to 1 l. in vacuo, dild. with EtOH, filtered, the filtrate concd., the sirup in 600 cc. 50%
EtOH shaken 8 hrs. at 100° with 10 g. Raney Ni under H at 3000 lb./sq. in., filtered, the filtrate deionized with Amberlite
IR-120 and Duolite A-4, and concd. in vacuo yielded a sirup, 4-D-glycero-2,2,4-tris(hydroxymethyl)-1,3-dioxolane (VI),
that did not crystallize. VI (21.3 g.) in 200 cc. 5N HCl refluxed 2 hrs. (the rotation, 4-dm. tube, changed from α20 D -1.58°
to 0°), the soln. decolorized, filtered, deionized, and concd. in vacuo yielded 11 g. glycerol tris(p-nitrobenzoate), m. 193-
5°. VI (4.6 g.) dried by heating with C6H6, mixed with 20 cc. Ac2O, cooled (ice bath), treated dropwise with 5 cc. H2SO4
(α20 D changed from -0.20 to +0.23°), the mixt. refrigerated 18 hrs., poured on ice, the acetylated products isolated with
CHCl3, deacetylated catalytically in MeOH with NaOMe, the product deionized, concd. in vacuo, dried by evapn. of C6H6,
the sirup tosylated 12 days at 20° (the expected tritosyl glycerol was not obtained), the sirup in 2:1 C6H6-C6H14
chromatographed on Al2O3 and eluted with the same solvent yielded 0.8 g. dichloro(tosyloxy)propane (VII), m. 65-7°,
optically inactive. Glycerol (3.7 g.), 22.3 g. tosyl chloride, and 100 cc. pyridine let stand 14 days at 20° and the mixt.
decompd. with ice gave 1.3 g. VII, m. 65-7°. II (28 g.), from I with Me2SO4 and NaOH (West and Holden, C.A. 28,
3058.5) m. 52-5°, [α]20 D -147° (water), in 300 cc. HNO3 (d. 1.42) heated to 90° during 5 hrs., heated 9 hrs. on the steam
bath, dild. with 1 vol. water, distd. in vacuo with the addn. of water until free of HNO3, the residue dried by distn. of abs.
EtOH, dissolved in abs. EtOH contg. 1% HCl, refluxed 9 hrs., cooled treated with Ag2CO3, concd. in vacuo, the sirup
extd. with Et2O, filtered, concd. in vacuo, the residue (15 g.) dissolved in C6H6-C6H14, the solvents evapd., the residue
dissolved in the same mixt., chromatographed on Al2O3, the 1st eluted fraction in 25 cc. MeOH satd. (ice bath) with
MeNH2, slowly warmed to room temp., let stand 60 hrs., the solvent removed in vacuo, the residue (a mixt. of several
types of crystals, 1.6 g.) in dioxane chromatographed on Al2O3, and eluted with C6H6 gave 1.41 g. of material which
yielded 30 mg. of N,N'-dimethyl-meso-2,3-dimethoxysuccinamide (VIII), m. 205-6°, [α]20 D -11.2 ± 2° (c 0.5, MeOH); the
mother liquor from VIII evapd. to dryness, and let crystallize slowly from 3 parts EtOAc yielded, on sublimation, 40 mg. III,
m. 165-70°, [α]20 D -70.1 ± 0.8° (c 1.2, MeOH). D-Arabinose (200 g.) in 900 cc. MeOH contg. 40 cc. concd. HCl refluxed
1 hr., the soln. seeded, cooled to room temp., and refrigerated overnight gave 46.2 g. Me β-D-arabinoside (IX), further
concn. of the filtrate brought the total yield to 175 g. Methylation of 13.5 g. of XI by the method of W. and H. (loc. cit.)
yielded 11 g. Me trimethyl-β-D-arabinopyranoside (X), [α]20 D -248° (c 1, water). X (10.7 g.) in 110 cc. HNO3 (d. 1.42)
heated 45 min. at 40-50°, 1 hr. at 60°, 1 hr. at 70°, and 2 hrs. at 95°, and the product converted to the methylamide as
above yielded 7.6 g. crude III which on recrystn. (EtOAc) gave III, m. 171-4°, [α]20 D -60.0° (c 1.3, water), and -66.2° (c
1.2, MeOH).
~5 Citings
164. Oxidative dissimilation of nonnitrogenous compounds in Acetobacter suboxydans

By King, Tsoo E.; Cheldelin, Vernon H.
From Science (Washington, DC, United States) (1952), 115, 14-15. Language: Unavailable, Database: CAPLUS,
DOI:10.1126/science.115.2975.14
Failure of A. suboxydans to oxidize acetate, form citrate, or acetylate sulfanilamide, even in the presence of an external
source of coenzyme A and adenosine triphosphate, indicates that citric acid cycle does not play a major role in the
oxidative metabolism of the organism. Diphosphopyridine nucleotide does not appear to be required either in the
oxidation of glycerol to dihydroxyacetone or ethanol to acetic acid.
~0 Citings

SciFinder® Page 90
165. Oxidative dissimilation in Acetobacter suboxydans
By King, Tsoo E.; Cheldelin, Vernon H.
cf. C.A. 46, 4059d; following abstr. Resting cells of A. suboxydans in phosphate buffer oxidized glycerol (I) with an O
consumption of approx. 4 atoms/mole of I. Oxidation of (HOCH2)2CO (II) required about 3 atoms/mole II. Yields of CO2
were 1.2-1.5 moles/mole of I or II. One mole of MeCOCO2H consumed 1 atom of O and produced 1 mole CO2.
MeCHOHCO2H was completely oxidized to AcOH and CO2. EtOH was oxidized to AcOH without CO2 formation.
Intermediates of the Krebs cycle, including citrate, α-ketoglutarate, succinate, fumarate, and acetate, were not oxidized in
either the presence or absence of small amts. of I. No acetylation of sulfanilamide or formation of citrate from acetate
and oxalacetate could be shown, even with added coenzyme A and adenosine triphosphate. Neither a C6 nor a C4 cycle
operates to a significant degree in this organism; the role of coenzyme A remains to be established.
~1 Citing
166. New di-D-fructose dianhydride

By Wolfrom, M. L.; Hilton, H. W.; Binkley, W. W.
DOI:10.1021/ja01131a043
Concd. HCl at -5° dehydrates D-fructose to yield in addn. to the previously reported di-D-fructopyranose 1,2':2,1'-
dianhydride (diheterolevulosan I) (I) and D-fructopyranose-D-fructofuranose 1,2':2,1'-dianhydride (diheterolevulosan II)
(II), the difructose anhydrides I (di-D-fructofuranose 1,2':2,1'-dianhydride) (III) and II (IV) of Jackson, et al. (C.A. 23,
4452), as well as a new dianhydride characterized as a hexahydrate and designated diheterolevulosan III (V). As
previously described (C.A. 46, 6089g), D-fructose was treated with 4 parts of concd. HCl for 72 hrs. at -5°. After removal
of I and II by fractional crystn. another fraction (Va) (9-12 g.) remained as a sirup. Va (2.5 g.) was chromatographed on a
column of 5:1 Florex-celite to give an effluent Ε (0.7-0.8 g.) and 3 zones on the column. Zones 1a and 2a were eluted
with EtOH-H2O to give 0.6-0.8 g. material. Zone 3a was similarly eluted to give 0.9-1.2 g. of solids, m. 240-5°
(decompn.). Seven such chromatograms were run. The material in zone 3a on purification gave the metastable form of
II, m. 258-61° (decompn.), [α]28 D -35.4° (c 3.8, H2O); hexaacetate was identical with an authentic sample in m. and
mixed m.p. and rotation. Ε (5.0 g.) was similarly chromatographed to give 2 principal zones: 1e was identified as glycerol
[tris(p-nitrobenzoate), m. 190-2°]; 2e (1.6 g.) was a sirup, [α]29 D 24° (c 4.6, H2O), which crystd. from EtOH to give 1 g.
IV, m. 204.5-8.0°, [α]30 D 13.1° (c 1.8, H2O). The mother liquors from IV gave 0.5 g. III, m. 158-9° (after acetylation and
deacetylation), [α]30 D 26° (c 1.6, H2O). 2e (500 mg.) was acetylated to give the hexaacetate of III, m. 125.5-7.0°,
resolidified and m. 138.5-9.0°, [α]26 D 1.6°, [α]26 5160 1.8°, [α]26 4960 2.1° (c 3.6, CHCl3). The combined material from
zones la and 2a was rechromatographed to give 1.1 g. of the stable form of I. Acetylation of I yielded the previously
reported hexaacetate (C.A. 28, 1333.3). V (1.52 g.) was also obtained from this chromatogram, m. 255-8°, [α]29 D -179°
(c 3.6, H2O). V was reduced only after acid hydrolysis. Periodate assay of V showed 3 moles of periodate consumed
with the formation of 1 mole of HCO2H and no HCHO, this behavior being identical with that of II; V hexaacetate, m.
135.5-6.5°, [α]25 D -169° (c 1, CHCl3). X-ray powder diffraction diagrams were recorded for all of the above mentioned
compds. Analysis of the optical rotatory data in the light of the Hudson isorotation rules suggests that II, IV, V, and di-D-
fructofuranose 1,2':2,3'-dianhydride (the difructose anhydride III of Jackson, et al., loc. cit.) contain the dioxane ring and
differ only in the anomerism of 1 of the 2 asymmetric centres in such a ring.
~3 Citings
167. Fat synthesis from small molecules

By Popjak, G.
From Biochemical Society Symposia (1952), No. 9, 37-51. Language: Unavailable, Database: CAPLUS
cf. C.A. 46, 7632e. The literature is reviewed and supplemented with some expts. with rabbits. It is concluded that the
building stone for fatty acid synthesis in animals is acetate and all of the constituents of the body which yield acetate
directly or indirectly can be converted to fatty acids. Glucose not only provides a substantial part of the acetate, but also
the glycerol required for fat synthesis. In rabbits the conversion of both glucose and pyruvate to acetate is so great, as
shown by the acetylation of p-aminobenzoic acid, that pyruvate probably does not act as a fatty acid precusor otherwise
than by previous decarboxylation to acetate. 38 references.
~0 Citings

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168. The constitution of pachyrrhizone
By Bickel, H.; Schmid, H.
From Helvetica Chimica Acta (1953), 36, 664-86. Language: German, Database: CAPLUS
Pachyrrhizone (I), m. 232-40° (decompn.) (open soft-glass tube), m. 250-1° (decompn.) (evacuated Pyrex tube), m. 272°
(no decompn.) (hot block), [α]20 D 100° (c 0.39, CHCl3), was isolated from Pachrrhizus erosus seeds and shown to be
identical with the product previously described in the literature (cf. Norton and Hansberry, C.A., 39, 53614; Meyer, C.A.
41, 2739f). I oxime, m. 279° (hot block); phenylhydrazone, m. 309° (decompn.) (hot block). I acetate formed in the
presence of NaOAc and refluxing Ac2O m. 147-8°. I was racemized by heating 1 hr. under N at the b.p. in Methyl
Cellosolve contg. NaOAc; the racemate m. 265° (hot block). I (100 mg.) dehydrogenated by heating in 4 ml. Methyl
Cellosolve contg. 200 mg. anhyd. NaOAc by adding 0.9 ml. 10% alc. iodine soln. gave dehydropachyrrhizone (II), m.
259-61°, also formed from I with K3Fe(CN)6. I in 20 ml. HOAc and 20 ml. CHCl3 treated in the cold with 3 ml. iso-
AmONO and 2.2 ml. concd. HCl in 3 ml. HOAc gave pachyrrhizonone (III), m. 343° (hot block). I degraded anaerobically
in hot aq.-alc. KOH gave an α-HO acid (IV), m. 196°. IV Me ether (V), formed with NaOH and Me2SO4, m. 130-30.5°. V
hydrogenated in HOAc with PtO2 at 26° and 722 mm. pressure gave the dihydro compd., m. 134.5-5.5°, identical with
synthetic 6,7-dimethoxycoumaran-5-carboxylic acid. IV decarboxylated by heating 15 min. at 250-70° in a sealed tube
and the product acetylated with boiling Ac2O gave 6-acetoxy-7-methoxycoumarone. Methylation of the decarboxylation
product of IV gave 6,7-dimethoxycoumarone (VI), isolated as the picrate, m. 62.5-3.5°. VI isolated from the mother
liquors from the recrystn. of the picrate m. 48.5-9.5°. IV at 20° in the dark with H2O2 in 5% aq. KOH gave (CO2H)2 and a
compd. which, after treatment with CH2N2, was characterized as di-Me 2,3-furandicarboxylate, m. 36.0-6.3°. IV heated in
a sealed tube at the b.p. of PhNH2 with C5H5N.HCl gave 6,7-dihydroxycoumarone, m. 65-72°, and 6,7-
dihydroxycoumarone-5-carboxylic acid, transformation at 190-210°, m. with decompn. and partial sublimation at 243-5°.
III heated 1 hr. anaerobically in 3% KOH soln. in H2O-Methyl Cellosolve gave a little IV and pachyrrhol (VII), m. 194-7°
after preliminary sintering. VII Me ether m. 173-4°; VII oxime, m. 215-17° (decompn.). VII in hot alc. KOH with H2O2
gave IV (6-hydroxy-7-methoxycoumarone-5-carboxylic acid). III heated under N with KOH in abs. EtOH gave IV,
(CO2H)2, and pachyrrhizol, m. 212-13°, a yellow compd. not further investigated. The synthesis of a no. of compds.
prepd. for comparison is given. 6,7-Dihydroxycoumaran (VIII), m. 110-11°, with NaOH and Me2SO4 gave the di-Me ether
(IX), b13 135-8°. IX heated 20 min. at 170-80° in a sealed tube in vacuo with Pd-Norit catalyst gave 6,7-di-
methoxycoumarone, m. 48.5-9°; picrate, m. 62.5-3.5°. VIII diacetate, prepd. with C5H5N-Ac2O, m. 116°. VIII heated 6
hrs. at 150-55° in glycerol with powd. KHCO3 with a continuous stream of CO2 passed through gave 6,7-
dihydroxycoumaran-5-carboxylic acid (X), m. 216-18° with decarboxylation (which begins at 200°). X di-Me ether m.
134.5-5.5°. 6,7-Dihydroxycoumaran-3-one (XI) heated 2 hrs. at 100° in Ac2O and AcCl gave 3,6,7-triacetoxycoumarone
(XII), m. 104-5°. XI heated 45 min. at 100° in Ac2O gave the 6,7-diacetoxycoumaran-3-one, m. 136.5-7°, which on
further acetylation gave XII. XII hydrogenated 8 min. at 22° and 723 mm. pressure in HOAc with PtO2 catalyst (1.1
moles H absorbed) gave 6,7-dihydroxycoumarone, m. 72.5-4°. 4,6-Dimethoxycoumaran-3-one heated 4 hrs. at 100° with
Ac2O gave 3-acetoxy-4,6-diethoxycoumarone (XIII), m. 70.5-71°. XIII hydrogenated like XII gave 4,6-
dimethoxycoumarone, isolated as the picrate, m. 93.5-4.5°. Ultraviolet and infrared spectra of the various compds. are
given.
~2 Citings
169. Synthesis and reactions of α-(3-methoxy-4-hydroxyphenyl)glycerol ("Guaiacylglycerol"). II. Synthesis

By Adler, E.; Yllner, S.
From Acta Chemica Scandinavica (1953), 7, 570-81. Language: English, Database: CAPLUS,
DOI:10.3891/acta.chem.scand.07-0570
SciFinder® Page 92
3,4-MeO(HO)C6H3CH(OH)CH(OH)CH2OH (I) was prepd. as a DL-mixt. by LiAlH4 reduction of 3,4 -
MeO(AcO)C6H3CH(OAc)CH(OAc)CO2Me (II); acetylation gave the 2 DL-tetra-Ac derivs. (III), and methylation gave 3,4-
(MeO)2C6H3CH(OH)CH(OH)CH2OH (IV), which was converted to the triacetate (V). Oxidation of I with NaIO4 was
studied. To 25 g. Me dibromohydroferulate in 150 cc. HOAc and 150 cc. Ac2O was added 2 cc. concd. H2SO4, the mixt.
let stand 24 hrs., poured into 2 l. ice H2O, the α,β-di-Br deriv. (VI), m. 146-7° (65% yield), sepd., recrystd. from EtOAc-
hexane, and 5.5 g. in 50 cc. HOAc heated 10 min. with 2.35 g. AgOAc, refluxed 3 min., the AgBr sepd., the solvent
evapd. in vacuo, the sirup dissolved in MeOH, filtered through kieselguhr, the filtrate concd. to 10 cc., and H2O added to
give 70% α-bromo-β-acetoxy-acetylhydroferulic acid (VII), m. 100-1° (from 80% MeOH and MeOH). VI (69 g.) in 600 cc.
HOAc and 500 cc. Ac2O refluxed 45 min. with 60 g. AgOAc, the AgBr sepd., washed with Me2CO, the washings and
filtrate concd. in vacuo to 300 cc., 400 cc. H2O added, the solvent evapd. in vacuo, the residue dissolved in CHCl3, the
soln. washed with NaHCO3 and H2O, dried over Na2SO4, evapd. in vacuo, and the residue dissolved in 100 cc. Et2O
gave 70% II, m. 109-10° (from EtOAc-hexane). II was similarly prepd. from VII. LiAlH4 (2.2 g.) heated under N in 300 cc.
Et2O until refluxing Et2O had dissolved 4.0 g. II from an extn. cup, heating continued 30 min., cooled, transferred under N
to a flask contg. 200 cc. cold N H2SO4, the aq. layer sepd., passed through an Amberlite IR-120 (H+) column, the effluent
neutralized with BaCO3, filtered, concd. in vacuo under CO2, filtered, further concd. in vacuo to 10 cc., H2O then
removed by addn. of EtOH and C6H6 and evapd. in vacuo, the residue taken up in 100 cc. Me2CO, and the soln. filtered
and evapd. in vacuo gave I, a clear, highly viscous sirup sol. in H2O, alcs., Me2CO, EtOAc, HOAc, and dioxane. I and
HOAc-Ac2O let stand 16 hrs., poured into H2O, the oil dissolved in Et2O, the Et2O soln. washed with 0.5 N H2SO4, aq.
NaHCO3, and H2O, dried over Na2SO4, concd., and a little hexane added yielded III, m. 84-5° (from EtOAc-hexane). The
consumption of periodate at 12° was detd. for I, guaiacol, and vanillin. The yields per MeO on treating an aq. soln. of I
with 0.7 M NaIO4 were HCHO 0.87, HCO2H 0.89, and vanillin (VIII) 0.54. CH2N2 in 50 cc. Et2O was added to 0.5 g. I in
10 cc. dioxane, then 50 cc. MeOH, the mixt. let stand 16 hrs., evapd. in vacuo, and residual solvents removed by addn.
of H2O and distn. in vacuo to give IV; oxidation of IV with NaIO4 at room temp. showed a consumption of 0.90
NaIO4/MeO, formation of 0.93 HCHO/2 MeO, and an 84% yield of veratraldehyde. CH2N2 was distd. from dioxane soln.
into 1 g. I in 50 cc. dioxane and 25 cc. MeOH, the solvents were removed in vacuo after 2 days and the oil acetylated
with 5 cc. pyridine and 5 cc. Ac2O to give V, which, distd. at 170°/0.05 mm., gave an almost colorless liquid mixt. of D-
and L-V. IV, m. 109-10° (C.A. 45, 9505d), acetylated as above gave cryst. V, m. 68-9° (from EtOAc-hexane). I (30 cc.
aq. soln. from 4 g. II) and 30 cc. aq. NaHSO3-SO2 at pH 3 and total SO2 content 10% heated 3 hrs. at 135°, Na+
removed on Amberlite IR-120, SO2 by concg. the mixt. to 200 cc. in vacuo, the concd. soln. neutralized with BaCO3,
filtered, concd. in vacuo to 5 cc., filtered through kieselguhr, EtOH and Et2O added, the solvent decanted, and the oil
treated with EtOH and washed with Et2O yielded 2.8 g. 1-(3-methoxy-4-hydroxyphenyl)-2,3-dihydroxy-1-propanesulfonic
acid (IX). A 5-cc. soln. of the crude product, contaminated with BaS2O3, acidified with H2SO4, distd. in vacuo to remove
SO2, neutralized with BaCO3, filtered, concd. in vacuo to a few cc., filtered Me2CO added, and the mixt. let stand in the
cold gave IX in fine needles. NaIO4 oxidation of IX gave 0.86 HCHO/IX, with a consumption of IO4 - exceeding 1
mole/mole IX, indicating oxidation of the phenolic nucleus.
~4 Citings
170. Synthesis and reactions of α-(3-methoxy-4-hydroxyphenyl)glycerol ("Guaiacylglycerol"). I. Preliminary

experiments
By Adler, E.; Bjorkqvist, K. J.
Me α,β-dibromohydroferulate (I) was prepd. and converted to the β-HO (II) and β-AcO analogs (III) acetylation of which
gave Me α-bromo-β-acetoxy-acetylhydroferulate [4,3-AcO(MeO)C6H3CH(OAc)CHBrCO2Me] (IV), in which the Br is
readily replaced by AcO, and which is inert to Br. I, m. 133-4° (decompn.), was prepd. in 76% yield by adding 77 g. Br to
100 g. cold Me ferulate in 250 cc. CHCl3 and sepg. the product, washing with CHCl3-hexane, and recrystg. from EtOAc-
hexane and C6H6-hexane. H2O (30 cc.) was added to 36.8 g. I in 200 cc. Me2CO or dioxane, the mixt. evapd. in vacuo
after 3 hrs., the oily residue dissolved in CHCl3, the soln. dried over Na2SO4, concd. in vacuo, and hexane added to give
15% II, m. 118-19° (from CHCl3 and C6H6). Acetylation of II with Ac2O and pyridine at room temp. gave IV, m. 100-1°;
the oily residue from the mother liquor of II, similarly acetylated, gave Me acetylferulate [4,3-
AcO(MeO)C6H3CH:CHCO2Me], m. 122-3°. Anhyd. KOAc (10 g.), 300 cc. HOAc, and 36.8 g. I let stand 24 hrs., the KBr
sepd., the soln. evapd. in vacuo, the residue taken up in C6H6, and the C6H6 soln. washed with H2O, dried over Na2SO4,
and dild. with hexane gave 15-20% III, m. 113-14° (from C6H6-hexane and C6H6). Acetylation with Ac2O-pyridine gave
IV, m. 100°, alone and mixed with IV from II. III (6.0 g.), 1.75 g. KOAc, and 100 cc. HOAc were heated 10 hrs. at 80°, the
mixt. concd. in vacuo, dild. with H2O, the oil which sepd. was extd. with C6H6, the C6H6 soln. washed with H2O, dried
over Na2SO4, concd., and hexane added to give impure unsatd. bromide, which was acetylated as above to give Me α-
bromoacetylferulate, m. 96-7° (from 80% MeOH and abs. EtOH). Unstable Me α-bromo-β-methoxyhydroferulate, m. 97-
8° (from MeOH-H2O), was prepd. from 15 g. I and 100 cc. MeOH let stand overnight at room temp., neutralized with
excess CaCO3, filtered, the filtrate dild. with H2O, extd. with CHCl3, the ext. dried, concd. to 25 cc. and hexane added, or
by passing dry HCl 1 hr. into a MeOH soln. of α,β-dibromohydroferulic acid (V) which had previously stood overnight. V,
m. 158-9° (from EtOAc-hexane), was prepd. by adding 32 g. Br in 250 cc. HOAc to 38.8 g. ferulic acid in 250 cc. HOAc
below 10°. To 50 g. V in 300 cc. HOAc and 300 cc. Ac2O was added dropwise 3 cc. concd. H2SO4, and the mixt. let
stand 2 days and poured on ice to give α,β-dibromo-acetylhydroferulic acid, m. 166-7° (from C6H6), 17 g. of which
refluxed in 400 cc. EtOH 8 hrs. with 12 g. KOAc, the KBr sepd., the soln. evapd., the residue dissolved in CHCl3, and the
CHCl3 soln. extd. with NaHCO3, washed with H2O, dried over Na2SO4, and evapd. gave β-bromo-3-methoxy-4-
acetoxystyrene, m. 109-10° (from MeOH).
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~2 Citings
171. Rapid acetylation of impregnated cellulose

By Thomas, John C.
DOI:10.1021/ja01117a059
Sol., high-mol. wt. cellulose triacetates have been prepd. in extremely short reaction times by the action of Ac2O at above
90° on cellulose impregnated with certain combinations of compds. from aq. soln. and dried. The 2 types of impregnants
were a swelling agent (urea) in 10-40% concn. (based on the cellulose) and a catalyst [(NH4)2SO4 (I)] in 1-10% concn.
Other compds. could be used in place of urea and I. Both types of impregnants were necessary, and their structural
requirements were detd. The following pairs of impregnants brought about rapid acetylation: urea with H2SO4, I,
NH4SO4, the sulfates of N2H4, PhNH2, Et2NH, piperidine (II), and morpholine (III), H2NSO3H (IV), the NH4, Et2NH2, and
III salts of IV, NH4OSO3Me, NH4OSO3C12H25, (NH4)2S2O8, (NH4)2SO3, (Et2NH)2SO3, (NH4)2S2O3, NH4 tetrathionate,
and OC(NHMe)2 with I, AcNH2 with H2SO4 or I, HOCH2CONH2 with I, HCO2NH4 with I, NH4OAc with I or NH2OH sulfate
or (CH2NH2)2H2SO4, HOCH2CO2NH4 with I, (CH2CH2CO2NH4)2 with I, ο-HOC6H4CO2NH4 with I, NH4SCN with I,
MeNH2.AcOH with (MeNH3)2SO4, PhNH2.AcOH with (PhNH3)2SO4, hexamethylenediamine adipate with I, Et2NH.AcOH
with I or (Et2NH2)2SO4, II acetate (V) with II sulfate, III acetate with III sulfate, Me2NCS2NH2Me2, H2O, glycerol,
(CH2OH)2, or (EtOCH2CH2)2O (VI) with I. Buckeye cotton linters (VII) (D.P. about 1850) contg. 4% moisture when
soaked 0.5 h. at room temp. in an aq. soln. contg. 38% urea and 2% I, the linters centrifuged to a wet wt. of 20 g., dried
in a vacuum desiccator over CaCl2 at room temp. (14 g.), boiled in 300 cc. Ac2O 90 s., poured with vigorous stirring into
2 l. 10% AcOH at 65°, and the ppt. agitated 15 min., filtered, washed with H2O, and dried at 65° gave 100% cellulose
triacetate with 2.97 Ac groups/glucose unit, 0.03 % combined sulfate, and a d.p. (D.P.) of 585. It was sol. in hot glacial
AcOH (not pptg. on cooling), sol. in CH2Cl2, and insol. in Me2CO. In a similar run at 95° for 18 min. 17 g. triacetate was
obtained with 2.91 Ac groups/glucose unit and 0.08% combined sulfate, D.P. 720, and the same soly. properties. Much
slower reactions took place when both activating agents were simply added to the Ac2O, or when VII was impregnated
with 1 agent and the other was added. VII impregnated with 39:1.5 AcNH2-IV from glacial AcOH did not react completely
with Ac2O within 1 h.; whereas VII impregnated similarly from H2O underwent rapid acetylation with boiling Ac2O.
Lowering the temp. to 95° increased the required reaction time (R.T.) and gave products of higher D.P.; below 90° the
acetylation either was incomplete or did not take place at all. Decreasing the urea concn. in the cellulose lowered the
D.P. and increased the R.T., the highest D.P. being obtained with 2% I at 138°. Increasing the concn. of I did not affect
the R.T. but lowered the D.P.; decreasing I below 2% lowered the D.P. and increased the R.T.; at 95° 1% I gave the
highest D.P. Urea was superior to all other impregnants tested. Although acetylation times as low as 15-30 s. were
realized with the acetates and sulfates of some primary and secondary amines at high catalyst concns., the products had
a lower D.P. than those of longer reactions involving urea-I. At equal mol. concns., H2SO4 and its salts had the same
activity, that of the corresponding derivs. of IV was the same or slightly lower. Lowering the amt. of Ac2O increased the
R.T. and decreased the D.P. VII and (EtCO)2O at 170° and at 95° gave cellulose tripropionates but the reaction was
slower than with Ac2O and gave products with lower D.P. (PrCO)2O was less reactive at 95° than (EtCO)2O; the highest
degree of esterification (D.E.) attained was about 2.6 PrCO groups/glucose unit. The anhydrides of CH2ClCO2H,
MeOCH2CO2H, Me3CCO2H, (CH2CO2H)2, ο-C6H4(CO2H)2, and maleic acid gave only very low D.E. Mixts. of Ac2O and
the anhydride of (CH2CO2H)2, ο-C6H4(CO2H)2, or maleic acid gave cellulose acetates with no other acyl groups.
Complete acetylation took place in dioxane, (ClCH2CH2)2O, MeNO2, ethylene carbonate, AcOH, and Et2SO4; AcOH and
Et2SO4 had degrading effects. A partial acetylation took place in trioxane, triacetin, BzH, CCl3CHO, and (CH2Br)2. The
acetylation of impregnated VII could also be carried out by a heterogeneous process in which a part of the Ac2O was
replaced by a nonsolvent for cellulose triacetate. This method had the advantage that the fibrous form of the linters was
preserved throughout, and the pptn. step was eliminated. Replacing part of the Ac2O by inert nonsolvents in this manner
increased the required R.T. and gave products of lower D.P., as in solvents for cellulose triacetate. The highest D.P.
(655) was attained in 50 min. in Me3CCHMeEt (VIII) at 97° with an 8:1 Ac2O-VII ratio. Acetylation proceeded faster in
VIII than in VI at 95°. Reactions in C6H6 at 89-93° were incomplete.
~0 Citings
172. Modification of vegetable oils. XIV. Properties of acetoöleins

By Feuge, R. O.; Gros, Audrey T.; Vicknair, E. J.
From Journal of the American Oil Chemists' Society (1953), 30, 320-5. Language: Unavailable, Database: CAPLUS,
DOI:10.1007/BF02636942
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cf. C.A. 47, 9032h. Pure 1,2-diaceto-3-olein (I) was prepd. by acetylating monoölein. A mixt. of acetoöleins was prepd.
by acetylating a mixt. of mono-, di-, and trioleins derived from com. oleic acid. Several natural oils were acetylated either
by ester-ester interchange with triacetin or by glycerolysis followed by acetylation. The phys. characteristics of the
compns. were compared. The I, which contains 19.5% of acetyl groups on the wt. basis, m. -18.3°, while the mixt. of
acetoöleins, which contained 14.3% of acetyl on the wt. bases, m. -24°. Acetylation of natural oils raises in most
instances their cloud and solid points and point of complete melting, but it also greatly increases their plasticity at lower
temps. A margarine-type fat prepd. by plasticizing hydrogenated cottonseed oil with aceto compds. was softer below
room temp. and harder above room temp. than butter, partially hydrogenated oil, or a blend of cottonseed oil and
hydrogenated cottonseed oil. The margarine-like product contg. 79% acetoölein and 18.5% highly hydrogenated
cottonseed oil had a constant consistency over the temp. range of -15 to 49°.
~1 Citing
173. Mode of synthesis of fatty acids from acetate and the conversion of carbohydrate into fat
By Popjak, G.
From Koninkl. Vlaam. Acad. Wetenschap., Letter. en Schone Kunsten Belgie, Kl. Wetenschap., Intern. Colloquium
Biochem. Problem. Lipiden (1953), 262-73. Language: English, Database: CAPLUS
Biosynthesis of milk fatty acids probably takes place in the mammary glands. Acetate mols. are condensed to form the
C-chain of the normal fatty acids. When a lactating goat was injected with a single dose of 5 mg. of C14-labeled acetate,
a definite relation between the specific activity and the chain length of the fatty acids was shown. In the first 12 hrs. the
specific activities increased in definite steps from butyric to decanoic (capric) acid; from 12 to 48 hrs., they increased
from butyric to myristic and palmitic acids. Some of the fatty acids were degraded chemically and the position of the C14
atom in the chain was detd. All results can be explained on the basis of the mode of biosynthesis. Cell-free
homogenates of rat mammary gland synthesize both short and long chain fatty acids from C14-acetate when incubated
aerobically in the presence of either of the 3 keto acids, pyruvate, oxalacetate, or α-ketoglutarate, and
adenosinetriphosphate. When the fatty acids from these homogenates were fractionated, the specific activities increased
stepwise from capric to palmitic acid. This indicates that the fatty acids in the mammary gland are synthesized by a
process analogous to a reversal of β-oxidation of fatty acids. Although no other intermediate than acetate has been
demonstrated in the biosynthesis of fatty acids, yet fat synthesis occurs in animals on a fat-free diet. It is possible that
some of the body's acetate is derived from the metabolism of carbohydrates. When C14-acetate or C14-starch or glucose
was given to rabbits 6 hrs. before milking, the distribution of labeled milk fatty acids was similar. The C14 content of
cholesterol was as high after feeding C14-starch as after C14-acetate. When p-aminobenzoic acid was fed with C14-
glucose or -acetate, the ratio of the specific activity of liver fatty acids and of liver cholesterol to that of the acetyl-C was
the same whether C14-acetate or C14-glucose was administered. Thus glucose might be converted to fatty acids after its
breakdown to acetate. Also, the specific activity of excreted acetyl-C was about 20% of that of lactose 6 hrs. after
administration of C14-glucose. The inference is that about 20% of the body's acetate used for acetylation is derived from
glucose. P. concludes that the synthesis of fatty acids from acetate proceeds by the stepwise condensation of C2 units,
and the conversion of glucose to fatty acids involves its previous breakdown to acetate, probably through pyruvate. Only
the C atoms 1, 2, 5, and 6 of glucose appear in fatty acids. The conversion of carbohydrate into fat means not only the
formation of fatty acids, but of the entire mol. including glycerol which appears to be metabolized by the body faster than
the fatty acids.
~0 Citings
174. Esterification of alcohols and cellulose with trifluoroacetic acid as a catalyst

By Morgan, Paul W.
CAPLUS
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The esterification of monomeric and polymeric alcs., especially cellulosic material, is accelerated by CF3CO2H (I). Thus,
freshly prepd. (hydroxyethyl)cellulose (II) (contg. 0.3 mole HOCH2CH2 groups/glucose unit) 1 was dried by solvent
exchange from H2O to AcOH, the II centrifuged until it contained AcOH 1, then added to Ac2O 4 and I 0.3 parts, the mixt.
heated 1.5 hrs. with stirring at 80°; the resulting clear, fiber-free, viscous soln., contg. 2.73 Ac groups/glucose unit, (sol. in
98% Me2CO and MeOH-CHCl3, gave clear though stable films from solns.), dild. with 50% aq. AcOH 10, heated 3 hrs.
with stirring at 80°, and pptd. with H2O gave secondary II acetate contg. 2.39 Ac groups/glucose unit, sol. in 98% Me2CO,
and giving clear, tough, stable films from solns. Similar acetylations of II for 2 hrs. without a catalyst and with
CH2ClCO2H and CCl3CO2H as catalysts introduced only 0.9, 0.88, and 1.46 Ac groups glucose unit. The speed of the
esterification in similar runs was proportional to the amt. of I present, as judged from the phys. properties of the product.
The esterification of II with EtCO2H in the presence of I at 100-30° gave similarly a II propionate contg. 2.72 EtCO
groups/glucose unit. An addnl. example for the acetylation of alkali-activated cellulose to a product contg. 2.92 Ac
groups/glucose unit is given. To pure glycerol 5 and Ac2O 30 was added at 30° I 0.065 part, the mixt. stirred 15 min., the
resulting homogeneous soln. stirred another 1.25 hrs. with cooling at 45-50°, and the volatile products were distd. off to
leave a nearly quant. yield of colorless glycerol triacetate. AmOH 44, glacial AcOH 30, and I 3.75 refluxed 1 hr. yielded
AmOAc 29 parts (43%), b. 145-8.5°; with azeotropic removal of the H2O during the reaction the yields was increased to
69.2%.
~3 Citings
175. Biosynthesis of milk fat in the rabbit from acetate and glucose. The mode of conversion of carbohydrate
into fat
By Popjak, G.; Hunter, G. D.; French, T. H.
From Biochemical Journal (1953), 54, 238-47. Language: Unavailable, Database: CAPLUS, DOI:10.1042/bj0540238
The biosynthesis of fat in lactating rabbits was studied by using acetate, pyruvate, and glucose labelled with C14. The
mammary gland synthesizes both short- and long-chain fatty acids, as well as cholesterol, from acetate or from glucose.
At least 30-70% of short-chain fatty acids originate in 6 hrs. from acetate and about 25% from glucose, but the amt. of
long-chain acids formed from these sources is only about 10-20% of the amt. of short-chain acids. Glucose gives rise
not only to fatty acids but also to glycerol, 65-95% of the glycerol part of the milk fat being formed newly in 6 hrs. by the
mammary gland from glucose. Likewise, 1/5 of the acetate used for acetylation of p-aminobenzoic acid comes from
glucose in well-fed lactating rabbits. It was found that the conversion of glucose to fatty acids proceeds by the over-all
reaction: glucose → pyruvate → acetate → fatty acid.
~0 Citings
176. Stabilizer for halogen-containing polymers

By Grummitt, Oliver J.; Blank, Robert E.; Schwarz, Herbert F.
CAPLUS
Polyvinyl chloride or other polyvinyl halide-contg. resin is stabilized with 0.1-10 parts per 100 parts of resin of partially
acylated glyceryl mono-ester of ricinoleic acid or of other fatty acids contg. 18-24 C atoms. The ester may be derived
from free acids or from oils, such as castor oil, by glycerolysis. The acylation radical may be acetyl or other acyl groups
contg. 1-6 C atoms. From 25 to below 75% of free OH groups of the ester are acylated. For example, 1868 g. castor oil
and 553 g. glycerol are heated to 160°, and 7.5 ml. Ca naphthenate soln. (contg. 5% Ca) is added. The mixt. is heated
and stirred for 3 hrs. at 210-215°, cooled to room temp., and glycerol is settled out in 1/2 hr. Glycerol is removed by
centrifuging to leave 2200 g. of glyceride of 13.8% OH content, which is then acetylated with 915 g. Ac2O at 160-5°, and
refluxed for 1/2 hr. The product is stripped of HAc in a Claisen distn. flask at 75-140°/30-40 mm. and finally at 140-50°/4-
6 mm. The hot residue is filtered by suction to remove Ca soaps, finally yielding 2470 g. of stabilizer of 5.3-5.7% OH,
sapon. no. 300-310, acid No. 1.0, Gardner color 6-9, and d25 25 1.20. When 3.0 parts of this stabilizer was incorporated
with 100 parts polyvinyl chloride and 50 parts dioctyl phthalate, a plastic resulted which, when milled and molded at 149°,
was of good heat stability (tested for 3 hrs. at 150° and 1/2 hr. at 174°) and of good light stability (21 days Eveready twin-
arc exposure test). In comparison, poor stability was observed in both these tests when the stabilizer was omitted.
~3 Citings
177. Plasticizing of cellulose esters or ethers

By Ito, Hisao
From No Corporate Source data available (1954), JP 29008297 19541215, Language: Unavailable, Database:
CAPLUS
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Cellulose acetate (56% acetylation) 10 and glycerol formal acetate 5 in Me2CO 120 parts form a transparent film with a
tensile strength of 4.30 kg./sq. mm. and an elongation of 33.98%.
~0 Citings
178. Lycoctonine: acid-catalyzed rearrangements

By Edwards, O. E.; Marion, Leo; McIvor, R. A.
From Canadian Journal of Chemistry (1954), 32, 708-17. Language: Unavailable, Database: CAPLUS,
DOI:10.1139/v54-091
The lactam derived from lycoctonine undergoes rearrangement on heating with mineral acids, forming
anhydrolycoctonam (I) by pinacolic dehydration. I then gives lycoctamone (II), m. 221-5° (from aq. MeOH), [α]20 D 274°
(c 2.0), by elimination of MeOH and hydrolysis of a MeO group. I (0.116 g.) in 2 cc. MeOH refluxed with 1 cc. 10% aq.
NaBH4 and the product acetylated overnight gave 0.083 g. dihydroanhydrolycoctonam diacetate, m. 174-7°, [α]25 D 33°
(c 1.8), after chromatography on Al2O3. Lycoctonam hydrate (0.500 g.) in 8 cc. 12N H2SO4 at 100° for 2 hrs. gave 0.260
g. II. I (0.040 g.) in 2 cc. 6N H2SO4, gently refluxed 5 hrs. under CO2, gave 0.025 g. II. II (0.108 g.) after 72 hrs. at 25°
with 2 cc. Ac2O in 2 cc. pyridine gave 0.072 g. lycoctamone monoacetate (III), m. 242° (from Me2CO), [α]D 192° (c 2.6),
after chromatography on Al2O3 (activity 4); at temps. around 115°, yields of 80% III were obtained. II (0.052 g.) with
0.030 g. NaBH4 in 2 cc. 50% aq. MeOH gave 0.046 g. lycococtamol (IV), m. 207-12° (from EtOAc), [α]25 D 212° (c 2.0);
0.020 g. IV in 3 cc. dry C6H6 and 2 cc. dry CHCl3 with 0.4 g. active MnO2 gave 0.011 g. II. III (0.250 g.) in 5 cc. MeOH
with 0.055 g. NaBH4 in 2 cc. H2O gave 0.090 g. lycoctamol monoacetate (V), m. 216-18° (from Me2CO-Et2O), [α]20 D
175° (c 2.7), after chromatography. IV and V acetylated overnight each gave lycoctamol diacetate, m. 177-80° (from
Et2O-petr. ether), [α]18 D 163° (c 1.84). II (0.045 g.) heated 1 hr. at 130° with 1 cc. glycerol and 0.5 cc. 85% N2H4.H2O
and the product refluxed 5 hrs. at 200° with 0.080 g. KOH gave 0.030 g. lycoctam (VI), feathery needles, m. 115-25°
(from aq. MeOH) [monoacetate, m. 151-9° (from Et2O-petr. ether)], [α]21 D 160° (c 3.2); 0.0271 g. II in 3 cc. EtOH contg.
3 drops concd. HCl with H over the Pt from 0.0102 g. Adams PtO2 gave 0.009 g. dihydrolycoctam (VII), needles, m. 182-
4° (from EtOAc), [α]21 D 85° (c 2.4), after chromatography. With molar uptakes of H varying from 2.6 to 3, the yield of VII
varied from 40 to 55%. Similarly, 0.029 g. IV gave 0.021 g. VII, and 0.0168 g. VI gave 0.0135 g. VII; 0.079 g. VII in 1 cc.
Ac2O and 1 cc. pyridine 45 hrs. at 25° gave 0.075 g. dihydrolycoctam acetate, m. 206° (from Me2CO-Et2O), [α]21 D 33° (c
1.9). All m.ps. are cor.
~2 Citings
179. Determination of dextran structure by periodate oxidation techniques

By Sloan, John W.; Alexander, B. H.; Lohmar, R. L.; Wolff, I. A.; Rist, C. E.
DOI:10.1021/ja01646a045
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The dextrans (I) produced by 6 strains of Leuconostoc mesenteroides were oxidized with NaIO4 and the proportions of
the various glucosidic linkages estimated by the sepn. and quant. detn. of structural fragments of the oxidized I. I from L.
mesenteroides NRRL B-512 was shown to contain 5% 1,3-linked anhydroglucose (II) units in addn. to the previously
recognized 95% 1,6-linked II units. Likewise, I from NRRL B-1064 yielded glucose, indicating 3% 1,3-linked units where
none were expected from the titrimetric NaIO4 analyses. The evaluation of the fragments obtained from NRRL B-1355 I
disclosed no evidence of 1,4-linkages. A new technique for isolating NaIO4-oxidized I has proved successful in
producing the polymeric dialdehydes (III) in high yields. The I from L. mesenteroides NRRL B-742 was fractionated by
pptn. between 41 and 90% EtOH to give a portion sol. in 41% EtOH (sol. fraction) which was sepd. from a portion pptd.
by 41% EtOH (insol. fraction). Preliminary oxidation with NRRL B-512 I were carried out by oxidizing all samples many
days at 25° in the dark, withdrawing periodically aliquots, and detg. the amt. NaIO4 consumed and HCO2H formed. The
oxidations of the I were carried out in glass-stoppered flasks protected from light; a weighed sample was slowly hydrated
with CO2-free distd. H2O and made to vol. including the specified amt. NaIO4; 1 sample of B-512 I was oxidized 44 days
at 25° and another sample 50 days at 1°; the preliminary oxidation of the sol. fraction of B-742 I showed comparable
yields of fragments at 63 and at 6 days. The NRRL no. of the L. mesenteroides forming the I, the % concn. I, the moles
NaIO4/mole II unit, the reaction times in days at 1°, and the mole-% yields of III, polyol, total fragments, and (adjusted to
100%) of glycerol, erythritol, and glucose (given in the indicated order) in these oxidation runs were: B-512, 1.0, 2.20, 50,
99.5, 75.6, 55.8, 95, 0, 5; B-742-sol. fraction, 0.2, 3.06, 6, 96.0, 76.8, 63.9, 64, 8, 28; B-742-insol. fraction, 0.4, 2.26, 17,
71.4, 61.8, 46.0, 95, 4, trace; B-523E, 0.4, 2.26, 6, 99.8, 65.0, 60.4, 93, 3, 4; B-1064, 0.4, 2.44, 6, 97.1, 80.0, 65.2, 95, 2,
3; B-1355, 0.4, 1.53, 6, 84.9, 84.8, 60.0, 53, 0, 47; B-1399, 0.4, 2.06, 6, 0.04, -, -, -, -, -. The oxidation mixt. treated with
160% 6N HCl followed by 150% aq. NaI, the resulting slurry poured into 10 vols. abs. EtOH with rapid stirring, the pptd.
gummy III washed 4-6 times with 95% EtOH on the centrifuge, the residue taken up in H2O, and the EtOH removed in
vacuo at 30-40° gave a soln. or gelatinous suspension of the III which was lyophilized or used directly in the next step.
The ultraviolet examination of the III soln. from B-512 I indicated no aldehyde absorption and the infrared examination
showed very little if any CO present although the presence of OH groups was indicated; the CO groups were apparently
masked by hydration. The III from B-512 I showed [α]25 D 171° (c 1.9, H2O), and inherent viscosity of 0.06, and a 1.8%
aq. soln. had pH 6.37. The III from B-742 sol. fraction showed [α]25 D 142° (c 1.0. H2O). The III were generally more
sparingly sol. in H2O than the original I; some required autoclaving. The III from B-512 I hydrogenated in a stainless
steel bomb at 100° and 1800-2000 lb. pressure 1 hr. over Raney Ni, the catalyst filtered and washed with boiling H2O,
and the combined filtrates made to vol. gave a polyol soln. having [α]25 D -8.1° (c 0.8, H2O); a portion of the soln.
lyophilized and the polyol (inherent viscosity 0.06) dried over P2O5, dissolved in pyridine, and heated 2 hrs. on the steam
bath with Ac2O gave the acetate deriv. contg. 40.8% Ac and showing [α]25 D 30.3° [(CHCl2)2]. The III from B-742 sol.
fraction gave similarly a polyol having [α]25 D 59.4°, which acetylated yielded an acetate deriv. with 41.5% Ac and
showing [α]25 D 60.5°. All polyols were shown to have no reducing power. The polyols chromatographed on paper gave
in the glycerol position spots only with I from B-523E and B-1064. An aliquot of a polyol soln. made N with H2SO4, and
the soln. heated 12-14 hrs. on a steam bath gave in all (except very dil. solns.) in 3-4 hrs. a brown color; the mixt.
adjusted with Ba(OH)2 to pH 6.5-6.7, digested 1-2 hrs. at 100°, and filtered, the filtrate concd. in vacuo, cooled, filtered,
and dild. to vol., and the soln. applied to Whatman No. 1 paper and chromatographed by descending irrigation with 6:4:3
BuOH-pyridine-H2O gave spots for glycerol, erythritol, and glucose. The hydrolyzate of the polyol from B-742-sol. I
decolorized with Darco G-60, streaked on Whatman No. 4 paper, and developed with BuOH-pyridine-H2O gave a
glucose band and a single zone contg. the erythritol and glycerol which was cut out, eluted, and rechromatographed to
sep. the components. Glucose was identified as the benzimidazole-HCl, m. 179-80°. Glycerol was characterized as the
tribenzoate, m. 72-3° (from aq. EtOH), and erythritol as the tetrabenzoate, m. 186-7° (from aq. pyridine).
~7 Citings
180. The estimation of the thioethoxy group of a sugar diethylmercaptal

By Hirase, Susumu; Araki, Choji
From Bulletin of the Chemical Society of Japan (1955), 28, 481-3. Language: English, Database: CAPLUS,
DOI:10.1246/bcsj.28.481
A convenient method for the detn. of thioethoxy groups in a sugar diethylmercaptal and its acetylated and methylated
derivs. in which the presence of SO4 -- groups does not interfere, has been established. A 0.1-0.2-g. sample is placed in
a flask attached to an app. of the type used for -OMe or -OEt detn., 10 cc. N HCl added, a stream of CO2 bubbled
through the soln., and the flask heated in a glycerol bath during 30 min. to boiling. The EtSH was liberated into excess
0.1N KI-I2 and EtOH soln., and after 2 hrs. the excess I2 was titrated. Excellent results are recorded for 7 sugars so
analyzed. With pentaacetyl-and pentamethyl-D-galactose diethylmercaptal, low results were obtained until 2 cc. glacial
AcOH was added to the hydrolyzing agent and heating was increased to 4 hrs.
~0 Citings
181. The action of alkali on D-fructose

SciFinder® Page 98
By Wolfrom, M. L.; Schumacher, J. N.
DOI:10.1021/ja01617a049
In an attempt to interpret in part the nature of the alk. defecation process in cane sugar-house work, an aq. soln. of D-
fructose (I) was heated 24 h. at pH 8 (initial) in the presence of aconitate ion. Chromatog. on clay of the deionized and
fermented reaction mixt. led to the isolation of D-glucuronic acid (II), allitol (III), and galactitol (IV) (III and IV after redn.
with H and Ni at low pressure and room temp.) and of (DL+D)-sorbose (V), identified in part by redn. and isolation of DL-
and L-glucitol (VI) and DL- and L-iditol (VII). Subsequent isolative cellulose sheet chromatog. led to the sepn. of
(DL+D?)-allose (VIII) and of DL-ribohexose phenylosazone (IX) of indicative DL-psicose (X) origin. While the origin of
the II is obscure, it is considered that the others probably arise by the reverse aldolization of D-fructose to trioses
followed by their recombination by aldolization, trans-Aconitic acid (34.8 g.) in 100 cc. H2O adjusted with aq. KOH to pH
8.00, the mixt. treated with 38 g. I, and the soln. dild. to 317 cc. and heated showed the following % absorption (T490 mµ,
Lumetron photoelec. colorimeter) and pH values at the times (in hrs.) indicated in parentheses: 98, 8.00 (0); 92, 7.50 (1);
50, 6.85 (2); 27, 6.65 (3); 19, 6.50 (4); 7, 6.38 (7); 4, 6.32 (9.5); 0, 6.15 (24). The resulting amber mixt. cooled to room
temp., dild. with H2O to 3000 cc., the soln. passed successively through Amberlite IR-120 cation exchanger and Duolite
A-4 anion exchanger, the effluent neutralized with aq. NaOH, fermented 120 h. at 28-30° with 22 g. starch-free bakers
yeast, and filtered with suction through Celite, the filtrate evapd. at 45-50° and 28 mm. pressure, the residual sirup (8.62
g.) dissolved in 100 cc. abs. MeOH, the soln. divided in 3 equal parts, each part dild. with abs. MeOH to 100 cc. and
chromatographed on a 23 × 7.5-cm. column of 600 g. 5:1 Florex XXX-celite (prewashed with 5000 cc. 95% EtOH and
conditioned further with 100 cc. abs. MeOH), the column developed with 1500 cc. 90% EtOH, extruded, wrapped in Al foil
to leave a 15-mm. free strip, dried 20 h., and streaked with aq. alk. KMnO4 (1 part in 100 parts 2.5N NaOH), the indicated
3 zones (top 18-45 mm., middle 67-201 mm., and bottom 210-30 mm.) sectioned, the top and bottom zone each eluted
with 1500 cc. 30% aq. EtOH and the middle zone with 3000 cc. 30% aq. EtOH, and the eluates evapd. gave 0.838, 4.09,
and 0.630 g. residue, resp., from the 3 zones; the effluent from the developed column gave 2.12 g., and the column top
0.290 g. material. I (40 g.) fermented with yeast and the fermn. residue chromatographed in the same manner gave no
zones on the column and only glycerol in the effluent. The sirup from the effluent kept in a desiccator over CaCl2 and
treated with a little abs. EtOH, the EtOH soln. decanted, the residual crystals dissolved in 4 cc. H2O and treated twice
with 15 mg. C for 5 min. at 50°, and the soln. evapd. gave V, m. 158.5-9.5°, [α]D 25 12.4° (c 2.9, H2O). V (500 mg.) in 50
cc. H2O hydrogenated 3 h. at 80° and 19 atm. pressure over 2 g. Raney Ni, the mixt. dild. with a small amt. EtOH and
filtered, the filtrate evapd. in vacuo, and the residual sirup dried over P2O5 during several weeks and treated with MeOH
yielded 200 mg. cryst. solid, fraction A; the mother liquor gave similarly 240 mg. solid fraction B. A recrystd. twice from
aq. MeOH gave DL-VI, fluffy white needles, m. 132-4°. A (100 mg.) acetylated 1 h. at 80° with 5 cc. Ac2O and 50 mg.
powd. NaOAc, the mixt. treated with 25 g. crushed ice and extd. with CHCl3, and the solid recrystd. from C6H6-petr. ether
yielded 151 mg. hexaacetate (XI)of DL-VI, m. 113-14°. B (240 mg.) acetylated in the same manner and the aq. mixt.
kept at 3° overnight gave 340 mg. fraction C, m. 155-63° (from C6H6petr. ether). The filtrate from C neutralized to pH 6
with solid NaHCO3 and extd. with five 10-cc. portions CHCl3, the ext. evapd., the residual sirup dissolved in C6H6, the
soln. treated with petr. ether and allowed to stand, and the cryst. deposit recrystd. from C6H6-petr. ether gave the hexa-
acetate (XII) of D-VII, m. 117-19°. The mother liquor from XII evapd., the residual sirup dissolved in C6H6, the soln.
treated dropwise with petr. ether to a faint turbidity, the solvent evapd. slowly, the liq. decanted from the solid, and this
process repeated 4 times gave a small amt. (5 mg.) of cryst. hexaacetate (XIII) of L-VI, m. 93-6°. XIII recrystd. with an
equal amt. of D-isomer from C6H6-petr. ether gave XI, m. 111-15°. C washed with abs. EtOH (the washings evapd. gave
XII) and recrystd. from C6H6-petr. ether gave the hexaacetate (XIV), m. 160-2°, of DL-VII. Hexaacetate of L-VII reduced
catalytically at room temp. and 7 lb. pressure in abs. EtOH over Raney Ni and acetylated gave keto-L-sorbose
pentaacetate, m. 118-19°. XII was prepd. similarly from keto-D-sorbose pentaacetate. Equal amts. D- and L-VII
recrystd. 3 times from C6H6-petr. ether yielded XIV, m. 162-3°. The top zone material (838 mg.) from the original
chromatogram in 5 cc. H2O treated with C and evapd. in vacuo, and the residual sirup crystd. from abs. MeOH with the
addn. of abs. EtOH at room temp. gave 42 mg. Na salt (XV) of II.H2O, m. 150° (decompn. with frothing), [α]D 24 21.5° (c
1.42, H2O). The middle zone (4.09 g.) gave a strong Seliwanoff ketose reaction and showed an apparent aldohexose
content of 30.4% by the Cajori hypoiodite assay; it had [α]D 38 3.2° (c 9.04, H2O); a portion (810 mg.) in 5 cc. H2O dild. to
150 cc. with abs. MeOH, the soln. hydrogenated 21 h. at 20 lb. pressure at room temp. over 4 g. Raney Ni, and the mixt.
worked up in the usual manner yielded 750 mg. mixed III and IV, m. 130-40° (from aq. EtOH). Mixed III-IV (100 mg.) and
500 mg. NaOAc heated to 100°, the resulting soln. kept 45 min. at 80°, cooled, poured onto 50 g. crushed ice,
neutralized to pH 6 with NaHCO3, and extd. with four 10-cc. portions CHCl3, the ext. evapd., the residual sirup distd.
repeatedly with C6H6 in vacuo, allowed to stand, and treated with 95% EtOH, and the cryst. material recrystd. from EtOH-
petr. ether yielded the hexaacetate (XVI) of IV, m. 140-50°; the 95% EtOH mother liquor allowed to stand several weeks
over CaCl2 and P2O5, and the resulting solid recrystd. from EtOH-petr. ether gave the hexaacetate (XVII) of III, m. 56-7°.
Middle zone (zone I) material (300 mg.) (5 cc. of a 6% aq. soln.) placed on 8 tapered Whatman No. 1 sheets (5.5 × 18
in.), this repeated until 2.75 g. had been added to about 70 sheets, the sheets developed descendingly 40-5 h. with
4:1.1:1.9 BuOH-EtOH-H2O, and the 5 zones (indicated with p-anisidine HCl salt in BuOH) eluted with H2O gave the
following sirupy fractions: Ia 210 mg. (ketose, yellow); Ib, 544 mg. (aldose, brown); Ic, 281 mg. (uronic acid, pink); Ia, 676
mg. (ketose, yellow); Ie, 202 mg. (uronic acid, pink). Small samples of each zone were rechromatographed in the same
manner parallel and simultaneously with known samples of cryst. VIII and amorphous X showed that Ib probably
contained VIII and Id probably X. Ib, [α]D 25 4.3° (c 2.24 H2O), kept in a desiccator, and the resulting mixt. of cryst. solid
and sirup treated with MeOH left cryst. DL-VIII, m. 180°. Id (200 mg.), 400 mg. PhNHNH2.HCl, and 600 mg. NaOAc in 4
cc. H2O heated 20 min. at 98°, the mixt. cooled to 0°, and the yellow-brown crystals recrystd. from abs. EtOH gave IX,
yellow crystals, m. 177-81° (decompn.). X-ray diffraction data are given for DL- and D-V, III, IV, VI, IX, XI, XII, XIII, XIV,
XV, and XVI.
~1 Citing
SciFinder® Page 99
182. The acetin method [for glycerol quality]

By Testorelli, Angel J. A.; Saguier, Ricardo A.; Bayer, Jose R.
From Anales direc. nacl. quim. (Buenos Aires) (1955), 8(No. 16), 60-4. Language: Unavailable, Database: CAPLUS
The following precautions were suggested to avoid errors in this acetylation: rapid weighing of sample (from wt. buret not
pipet), sealed ampuls for adding Ac2O, U.S.P. quality petrolatum for stoppers, etc., carefully timed heating to prevent loss
of acetylated product as well as careful mixing to prevent carbonization or drying of salts on the walls of the flask during
heating. Water added after heating should be exactly at 80°, and heating should be avoided during neutralization of the
acetylate, by running alkali down the side of the flask. Results should be corrected for acetylizable material in the total
residue. Results of replicate detns. agree to 0.5% in the hands of experienced analysts.
~0 Citings
183. Some chlorinated hydroxyphenoxyacetic acids

By Brown, J. P.; McCall, E. B.
DOI:10.1039/jr9550003681
SciFinder® Page 100
Efforts to det. the fate of 2,4-Cl2C6H3OCH2CO2H in plants and in soil substrates led to the present syntheses of various
chlorinated (hydroxyphenoxy)acetic acids. A metabolite isolated from cultures of bacteria grown in a medium contg. 4-
ClC6H4OCH2CO2H [Evans and Smith, Biochem. J. 57, No. 4, xxx(1954)] was believed to be 4,2-Cl(HO)C6H3OCH2CO2H
(I), so its synthesis was first undertaken. 4-ClC6H4OCH2CO2H (10 g.) heated 2 h. at 90° with 100 mL. concd. HNO3
gave 7.0 g. 4,2-Cl(O2N) C6H3OCH2CO2H (II), m. 173-5° (from aq. MeOH); II (1.0 g.) reduced with Na Na2S2O4 at 90°
and acidified to pH 4 gave 0.15 g. white needles, m. 215-18°, and the filtrate boiled with 32% HCl yielded 0.52 g. of the
same material. This was the lactam of 4,2-Cl(H2N)C6H3OCH2CO2H, 6-chloro-3,4-dihydro-3-oxobenzoxazine, m. 217-18°
(from EtOH). II (5.0 g.)was also boiled in 50 mL. C6H6, with 8.0 mL. SOCl2, 8 h., the C6H6 and excess SOCl2 evapd., 4.0
g. 20% soln. of NHMe2 in C6H6 added to the residue, and the mixt. allowed to stand overnight, then concd., and filtered,
giving 4.7 g. crude 4,2-Cl(O2N)C6H3OCH2CONMe2, m. 84° (100-1° on recrystn. from MeOH), reduced by Fe and HOAc
in aq. EtOH to the 2-H2N analog, m. 121° (from EtOH). Attempts to replace the NH2 group by OH in both the NH2 acid
and its dimethylamide failed. 5,2-Cl(HO)C6H3Ac (2.8 g.) boiled 4 h. with 3.2 g. NaOH and 4.7 g. ClCH2CO2H in 30 mL.
H2O, cooled, and acidified gave 2.4 g. 4,2-ClAcC6H3COCH2CO2H, m. 177-8° (from aq. MeOH). Efforts to oxidize this to
I were unsuccessful. 4,1,2-ClC6H3(OH)2 (14.8 g.) added to a soln. of 2.8 g. Na in 60 mL. dry EtOH and the boiling mixt.
treated with 3.7 g. ClCH2CO2Et, gave 6.4 g. impure 5,2-Cl(HO)C6H3OCH2CO2H, m. 157° (from H2O), forming with
Me2SO4 and hot 20% aq. NaOH with a Me ether (III), m. 143-5° (from aq. MeOH). The identity of III was established by
first reducing 4-nitroguaiacol with H at room temp. and atm. pressure over Pd-C to the amino compd., converting it to the
HCl salt, diazotizing, and adding CuCl to give 4-chloroguaiacol, m. 36-7°, which, allowed to react with ClCH2CO2H in
NaOH and H2O 2 h. at 95°, then acidified, gave 5,2-Cl(MeO)C6H3OCH2CO2H, m. 141-3° (from C6H6), identical with III.
4-Nitroguaiacol and ClCH2CO2H condensed in the presence of NaOH to either 2,5-HO(O2N)C6H3OCH2CO2H (IV), m.
191° (from aq. MeOH), or the 2-MeO analog (V), m. 180-2° (from aq. MeOH), depending on the concn. of NaOH used.
IV reduced, diazotized, and treated with CuCl as above gave 5,2-Cl(HO)C6H3OCH2CO2H, m. 157° (from H2O and aq.
MeOH), and V gave first 5,2-H2N(MeO) C6H3OCH2CO2H, m. 232° (from H2O), and finally 5,2-Cl(MeO)C6H3OCH2CO2H,
m. 140-2° (from aq. MeOH). 5-Nitroguaiacol converted to 5-chloroguaiacol, m. 16-17°, as described above for the 4-Cl
compd., then treated with ClCH2CO2H, yielded 4,2-Cl(MeO)C6H3OCH2CO2H, m. 135-6° (from C6H6 or aq. MeOH), which
(0.2 g.), boiled 1 h. with 2.0 mL. 48% aq. HBr, gave on cooling 0.15 g. I; after recrystn. from H20, slowly I, m. 110° on
slow, 124-30° on rapid heating. 5-Nitroguaiacol (2.0 g.) with 1.5 g. ClCH2CO2Et in the presence of NaOMe gave 0.5 g.
2,4-MeO(O2N)C6H3OCH2CO2Et, m. 88-91° (from MeOH). 3,5,1,2-Cl2C6H2,(OH)2 and ClCH2CO2Et gave 2,4,6-
Cl2(HO)C6H2OCH2CO2H (VI), m. (depending on the rate of heating) 130-55° (after recrystn. from H2O), identical with the
substance prepd. by Cavill and Ford (C.A. 49, 3072h). Its Me ether, m. 174-6°. 2,4-Cl2C6H3OH nitrated with concd.
HNO3 at 30-40° to 2,4,6-Cl2(O2N)C6H2OH, m. 122-4°, then reduced in alk. Na2S2O4, neutralized with HOAc, and the
resulting aminophenol acetylated with Ac2O yielded 4,6,2-Cl2(AcNH)C6H2OH, m. 138-40° (from aq. EtOH), which, boiled
6 h. in acetone with MeI and K2CO3, formed 4,6,2-Cl2(AcNH)C6H2OMe, m. 112-14° (from light petroleum, b. 60-80°),
hydrolyzed by boiling 1 h. in 20% HCl to 4,6,2-Cl2(H2N)C6H2OMe.HCl, m. 196° (from dil. HCl), converted with NaOH to
the amine, f.p. 16°. The amine diazotized and the diazonium soln. added to CuSO4 in H2O with simultaneous passage of
steam yielded from the steam distillate 4,6-dichloroguaiacol, m. 63-4° (from light petroleum, b. 60-80°), converted in the
usual way into 3,5,2-Cl2(MeO)C6H2OCH2CO2H, m. 106-7° (from PhMe). The MeO acid, boiled 1 h. with 48% HBr gave
3,5,2-Cl2(HO)C6H2OCH2CO2H, m. 154° (from H2O). 2,4-Cl2C6H3NH2 (12 g.) in 450 mL. acetone and 700 mL. H2O
contg. 11 g. KOH treated during 5 h. at 25° with 20 g. K2S2O8 in 450 mL. H2O gave only 1.5 g. product which, boiled with
20% HCl, basified with NaHCO3, and Ac2O added yielded 0.4 g. 3,5,2-Cl2(AcNH)C6H2OH, m. 190-3° (from aq. MeOH),
methylated with MeI to 3,5,2-Cl2(AcNMe)C6H2OMe (VII), m. 107-9° (from light petroleum, b. 60-80°). This route to 3,5-
dichloroguaiacol was abandoned, though, because of the poor yields in these 2 steps. When 9.0 g. 5-chlorovanillic acid
in 90 mL. glycerol contg. 0.2 g. Cu bronze was heated 10 min. at 250-60°, and steam was passed through the mixt., 1.7
g. 3-chloroguaiacol, m. 54° (from light petroleum, b. 60-80°) was recovered from the distillate; a C6H6 soln. of this compd.
did not react with SO2Cl2 at room temp., and boiling with a large excess of SO2Cl2 gave a mixt. from which 5% of a
trichloroguaiacol, m. 102-4° (from light petroleum, b. 60-80°) was isolated. 5-Chlorovanillic acid (5.0 g.) was dissolved in
30 mL., warm concd. H2SO4, 50 mL. CHCl3 added, and the mixt. stirred at 45° while 2.5 g. NaN3 was added during 30
min., then poured onto ice, and filtered. If the filtrate was basified at this point, it gave a rapidly discoloring ppt. of 5-
amino-3-chloroguaiacol which could be converted by the addn. of Ac2O into 5-acetamido-3-chloroguaiacol, m. 165° (from
H2O). To obtain 3,5-dichloroguaiacol, the filtrate was treated with BaCl2 soln. to remove the sulfate, and the remaining
amine hydrochloride soln. diazotized and treated with urea and a soln. of CuCl2; steam distn., extn. with Et2O, and
vacuum-distn. gave 0.3 g. material, b15 170° (bath temp.), which, recrystd. 3 times from light petroleum (b. 60-80°), gave
3,5-dichloroguaiacol (VIII), m. 64-5°, also obtained from 2,4,6-Cl3C6H2NO2 by condensation with NaOMe to 3,5,6-
Cl2(O2N)C6H2OMe, m. 70-2° (from EtOH) and redn. with H (Raney Ni) to 3,5,2-Cl2(H2N)C6H2OMe (IX). Acetylation of IX
gave the N-Ac deriv., m. 169.5-71.5° (from PhMe), and methylation gave VII. IX in concd. H2SO4 converted into VIII as
described in the diazotization of the 4,6-Cl2 isomer. VIII (0.6 g.) yielded in the usual way 0.7 g. VI, identical with the acid
from 3,5,1,2-Cl2C6H2(OH)2. 2-ClC6H3OCH2CO2H boiled with concd. HNO3 5 min. gave the 4-O2N deriv., m. 179-81°
(from aq. EtOH), esterified with MeOH and. concd. H2SO4 to the Me ester, m. 124°. Hydrogenation of the ester in MeOH
over Pd gave 2,4-Cl(H2N)C6H3OCH2CO2Me, m. 69° (from petr. ether, b. 60-80°), which was diazotized, added to CuSO4
in boiling H2O, the product extd. with Et2O, dissolved in NaOH, pptd. with acid, dried, treated with boiling C6H6, and the
fraction insol. in C6H6 recrystd. twice from H2O to give 2,4-Cl(HO)C6H3O CH2 CO2H acid (X), m. 146-7° [Me ether, m.
136-8° (from PhMe)]. Another synthesis of X involved chlorinating p-MeOC6H4OH with SO2Cl2 to 2,4-Cl(MeO)C6H3OH,
b15 108°, m. 46-7° (from petr. ether, b. 60-80°), and converting this in the usual way to a phenoxyacetic acid, which was
identical with the above 2,4-Cl(MeO)C6H3OCH2CO2H and on boiling with 48% HBr gave X. A bacterial metabolite of 2,4-
Cl2C6H3OCH2CO2H has been isolated by Evans which is not identical with any of the hydroxyphenoxyacetic acids
described above.
~5 Citings

184. Reduction of the products of periodate oxidation of carbohydrates. I. Hydrogenation with Raney nickel of
the dialdehydes from the methyl glucopyranosides
By Smith, F.; Van Cleve, J. W.
DOI:10.1021/ja01616a047
It has been shown that the dialdehydes obtained from sugar glycosides by oxidn. with HIO4 can be reduced readily to the
corresponding alcs., the structure of which has been proved. Since this treatment results in the elimination of all
dissymmetry except that at C-1, and examn. of these new alcs. provides a simple way of correlating the structure of the
glycosides. The appropriate Me α-D-hexopyranoside (2.5 g.) (I) in 150 cc. H2O treated with 70 cc. N HIO4, dild. quickly
to 250 cc., shaken to uniformity, kept 2-4 h. at room temp. until the optical rotation had assumed a const. value, and an
aliquot titrated with Na arsenite showed that in all cases 2 mol HIO4 had been consumed/mol I. The aq. reaction mixt.
neutralized with satd. aq. Ba(OH)2 towards phenolphthalein, the excess Ba(OH)2 neutralized with Dry Ice, the pptd. Ba
salts filtered off, washed with H2O, and evapd. to dryness in vacuo, the residue extd. with large amts. abs. EtOH at room
temp., the soln. clarified with activated C, and the filtrate evapd. in vacuo gave D-hydroxymethyl-D'-methoxydiglycolic
aldehyde (II), clear sirup, which gave a rather weak and slowly developing Schiff test and a neg. Fehling test. The β-
anomers of I gave similarly the L'-isomer (III) of II. The II in 70 cc. abs. EtOH hydrogenated 5-6 h. at 110-20° and 1000-
2000 lbs. pressure over 1.5-2 g. Raney Ni, the mixt. cooled, treated with activated C, and filtered, the filtrate evapd. to
dryness in vacuo, and the residue (transferred with MeOH) distd. in a high vacuum gave D-hydroxymethyl-D'-
methoxydiethylene glycol. (IV), clear, viscous, colorless sirup, b0.001 170-80°, in 80% yield or better. III gave similarly the
L-isomer (V) of IV. The II (1.45 g.) from Me α-D-glucopyranoside, [α]D 20 155.4° (H2O), in 50 cc. H2O treated during 1 h.
with NaBH4 in portions showed the following changes in rotation at the times in min. indicated in parentheses: 2.45° (5),
1.25° (15), 0.5° (20), 0.06° (30), 0.06° (60), -0.36° (120). The soln. kept a further hr. at room temp., neutralized with CO2,
and evapd. to dryness in vacuo at 35-40°, the residue extd. with hot EtOH, the resulting turbid soln. cooled and
centrifuged, and the clear soln. evapd. to dryness in vacuo gave 1.1 g. IV, colorless liq., b0.001 175°, nD 22 1.4650, [α]D 20
- 10° (c 2.2, H2O). IV (0.15-0.20 g.) in 5 cc. dry pyridine heated 0.5 h. at 80-90° with 0.5 cc. BzCl, the mixt. cooled to
beginning crystn., poured into 20 cc. satd. aq. NaHCO3, and extd. after a few min. with two 20-cc. portions CHCl3, the
ext. washed 3 times with large amts. of H2O, dried, and evapd. in vacuo, the residue treated with a little petr. ether,
seeded, and allowed to stand overnight, and the crude product (about 0.5 g.) recrystd. 2-3 times from CHCl3-petr. ether
gave tri-O-benzoate (VI) of IV, m. 66-7°. V gave similarly a tri-O-benzoate (VII) of V, m. 66-7°. IV (0.16 g.) in 5 cc. dry
pyridine heated 0.5 h. with 0.80 g. p-O2NC6H4COCl (VIII) at 80-90° and the mixt. worked up as for VI gave 0.35 g. crude
tri-O-(p-nitrobenzoate) (IX) of IV, m. 110°. V gave similarly the tri-O-(p-nitrobenzoate) (X) of V. A variety of I was
subjected to this sequence of transformations {I, [α]D 20 (H2O), [α]D 20 (H2O) of II (or III), [α]D 20 (EtOH) of IV (or V), nD 20
of IV (or V), [α]D 20 (EtOH) of VI (or VII), and [α]D 20 (CHCl3) of IX (or X) given}: Me α-D-glucopyranoside, 155.4°, 121.1°,
-9.9°, 1.4660, -21.6°, -23.5°; β-anomer, -30.3°, -141.1°, 11.4°, 1.4650, 21.8°, 24.2°; Me α-D-mannopyranoside, 79.0°,
121.5°, -8.6°, 1.4655, -20.2°, -24.6°; β-anomer iso-Pr alcoholate, -51.1°, -145.9°, 10.7°, 1.4648, 22.4°, 25.0°; Me α-D-
galactopyranoside monohydrate, 172.8°, 118.4°, -10.3°, 1.4652, -21.3°, -24.3°; Me β-D-galactopyranoside, 0.0°, -144.1°,
10.8°, 1.4650, 21.1°, 24.2°. IV (or V) (0.15 g.) in 3 cc. aq. N HCl kept 15 min. at room temp., the resulting inactive soln.
neutralized with NaHCO3 and evapd. to dryness in vacuo, the residue extd. with abs. EtOH, the ext. evapd. to dryness in
vacuo, the residue dissolved in 5 cc. dry pyridine, the soln. heated 20 min. at 80-90° with 0.76 g. VIII on the water bath,
the mixt. cooled, poured into 20 cc. satd. aq. NaHCO3, and filtered, the filter residue washed with H2O and dissolved in
100 cc. CHCl3, the soln. dried, decolorized with C, concd. to a small vol., treated with petr. ether to turbidity, and seeded,
and the resulting deposit (0.31 g.) recrystd. from CHCl3-petr. ether and then from hot EtOAc gave glycerol tris-O-(p-
nitrobenzoate), m. 197.5°. VI (or VII) (0.09 g.) in 2.75 cc. glacial AcOH treated with 0.25 cc. concd. HCl, the resulting
optically inactive soln. treated after a few min. with 0.05 g. 2,4-(O2N)2C6H3NHNH2, and the cryst. deposit (0.05 g.)
recrystd. from CHCl3-petr. ether gave 2,4-(O2N)2C6H3NHN:CHCH2OBz, m. 188.5°. The carefully purified Me α-D-
pentopyranoside oxidized in the same manner as described for the I consumed 2 mol HIO4/mol; the aq. soln. worked up
in the usual manner gave D-OHCCH2OCH(OMe)CHO (XI). The β-anomer gave similarly the L-isomer (XII) of XI. XI in
abs. EtOH hydrogenated in the usual manner over Raney Ni gave 80% (or better) D-HO(CH2)2OCH(OMe)CH2OH (XIII).
XII gave similarly the L-isomer (XIV) of XIII. Me α-D-xylopyranoside (10 g.) in 600 cc. H2O treated with 2.4 g. NaBH4, the
excess NaBH4 decompd. with CO2, the soln. concd. in vacuo, the residual sirup extd. with EtOH, the ext. evapd. in
vacuo, the residue treated with MeOH, the MeOH removed in vacuo, this process repeated 4 times, and the residue
distd. yielded 5.5 g. XIII, colorless liq., b0.001 130-40°, nD 24 1.4443, [α]D 20 -6.9° (c 0.6, EtOH). XIII acetylated with Ac2O-
pyridine gave 100% di-O-acetate, colorless liq., b0.001 105-7°, nD 25 1.4286, [α]D 0° (CHCl3), which treated with NaOMe
gave XIII, b0.005, 112-14°, nD 26 1.4432, [α]D 23 -7.5° (c 2.0, EtOH). XIII (or XIV) (0.15 g.) in 3 cc. N aq. HCl allowed to
stand 15 min. until it became optically inactive, the soln. neutralized with aq. NaHCO3 and evapd. to dryness in vacuo at
40-5°, the residue dissolved in 5 cc. dry pyridine, the soln. heated 15 min. at 80-90° with 0.61 g. VIII, the mixt. cooled,
poured with stirring into 40 cc. satd. aq. NaHCO3, and filtered, the filter residue washed with H2O, dried, and dissolved in
CHCl3, the brownish soln. decolorized with activated C and evapd. to dryness in vacuo, the residual sirup extd. with hot
EtOH, and the ext. concd. to a small vol. and dild. with Et2O pptd. (p-O2NC6H4CO2CH2)2, m. 146°. XIII (0.16 g.) in 5 cc.
dry pyridine heated 45 min. with 0.60 g. VIII at 80-90°, and the mixt. poured into 20 cc. satd. aq. NaHCO3 and worked up
in the usual manner gave the p-nitrobenzoate (XV) of XIII, m. 112-13° (from CHCl3-petr. ether). XIV gave similarly the p-
nitrobenzoate (XVI), m. 112-13°. A no. of Me pentopyranosides (XVII) was subjected to the general oxidn. and redn.
procedure [XVII, [α]D 20 (H2O), [α]D 20 (H2O) of XI (or XII), [α]D 20 (EtOH) and nD 20 of XIII (or XIV), and [α]D 20 (CHCl3) of
XV (or XVI) given]: Me α-D-xylopyranoside, 149.4°, 122.6°, -6.9°, 1.4410, -10.0°; β-anomer, -63.0°, -122.0°, 7.5°, 1.4410,
11.4°, Me α-L-arabinopyranoside, 19.7°, -122.4°, 6.8°, 1.4418, 10.8°; β-anomer, 235°, 122.7°, -6.9°, 1.4421, -10.2°. XV
(or XVI) (0.08 g.) in 2.75 cc. glacial AcOH treated with 0.25 cc. concd. HCl and then 0.55 g. 2,4-(O2N)2C6H3NHNH2, and
the yellow ppt. washed with a little glacial AcOH and Et2O, and recrystd. from CHCl3-petr. ether gave the 2,4-
dinitrophenylhydrazone of p-O2NC6H4CO2CH2CHO, m. 189-90°.
~3 Citings
185. Plasticizers of pentaerythritol and oil or fat

By Shino, Yoshihiro; Omori, Sugio; Komori, Saburo
From No Corporate Source data available (1955), JP 30007730 19551024, Language: Unavailable, Database:
CAPLUS
The mixts. of pentaerythritol and polyalcs., such as glycerol or sorbitol, were caused to react with fat or oil so that more
than 1 unreacted hydroxy group remained in a mol. and then the hydroxy groups were acetylated with lower org. acids,
such as acetic acid, or their anhydrides. The products were excellent plasticizers. Thus, a mixt. of pentaerythritol 3,
glycerol 22, palm oil 50, and KOH 0.5 part was heated at 200° under an atm. of CO2 and with agitation. After cooling, 45
parts acetic anhydride was added, and the mixt. was heated at 110° for 1 hr. while blowing with H.
~0 Citings
186. Glyceride synthesis. I. Synthesis of symmetrical diglycerides from dihydroxyacetone and allyl alcohol
By Barry, P. J.; Craig, B. M.
DOI:10.1139/v55-087
(EtO2CCH2)2CO (I), m. 60-60.5° [prepd. in 54% yield from (EtCO)2O and (CH2OH)2CO in C5H5N], (5 g.) held 24 hrs. in
an ice-salt bath with 50 ml. EtSH and 2.5 g. ZnCl2 yielded 91% of I di-Et mercaptal (II), nD 1.4966, b6 157-8°, isolated by
pouring the reaction mixt. into satd. NaHCO3 soln., extg. with Et2O, and distg. the dried Et2O layer. Interesterification of
3 g. II with 6 g. Me stearate (III) contg. 0.3 ml. satd. NaOMe in MeOH on a steam bath in vacuo gave 77% (5.6 g.)
(C17H35CO2CH2)2C(SEt)2 (IV), m. 49.1-9.4°, upon extn. of the reaction mixt. with Et2O. Similarly, 81% (n-
C15H31CO2CH2)2C(SEt)2 (V), m. 39.5-40.0° (from Me2CO), was obtained from II. IV and V were converted to 1,3-
distearoxy (VI), m. 87-7.5°, and 1,3-dipalmitoyloxyacetone (VII), m. 82-2.5° (Schlenk, et al., C.A. 48, 11336e reports 77-
8°), resp., when refluxed with HgCl2 in aq. Me2CO. Hydrogenation of VII and VI in tetrahydrofuran over Raney Ni 3 hrs.
at 50 lb./sq. in. and at room temp. produced almost quant. yields of 1,3-dipalmitin (VIII), m. 72.0°, and 1,3-distearin (IX),
m. 78.5-9°. I was converted to 22% I di-Et ketal, nD 25 1.4926 with HC(OEt)3, EtOH, and p-MeC6H4SO3H. Allyl
tetrahydropyranyl ether (X), b. 165-7° (over NaHCO3), nD 25 1.4421, was prepd. in 78% yield by shaking 17 g. 2,3-
dihydropyran (XI) with 11.5 g. allyl alc. contg. 1 drop conc. HCl 3 hrs. at room temp. X (106.5 g.) oxidized with 120 g.
KMnO4 in 3 l. H2O 2 hrs. at 5° and 1 hr. on the steam bath, filtered, the filtrate satd. with K2CO3, extd. with Et2O, the ext.
evapd. yielded 102 g. (66.5%) crude 1-tetrahydropyranylglycerol (XII), b4 146-9°, nD 25 1.4736 (quant. reaction with
HIO4). Acetylation of XII with Ac2O in C5H5N gave 50% 2,3-diacetoxy-1-tetrahydropyranylglycerol (XIII), nD 25 1.4456. IX
was prepd. (64%) from XII with stearoyl chloride in dry C5H5N-CHCl3 and by the interesterification of XIII with III. X was
prepd. similarly but no details are given. Glycerol is reported not to form a monoacetal with XI.
~2 Citings
187. Epoxy esters as plasticizers and stabilizers for vinyl chloride polymers
By Witnauer, Lee P.; Knight, H. B.; Palm, W. E.; Koos, R. E.; Ault, W. C.; Swern, Daniel
DOI:10.1021/ie50551a034
Epoxidized diacetomonoglycerides (produced by interesterification of fats (I) with triacetin, followed by epoxidation with
MeCO3H) are good plasticizers and light stabilizers. I used were: tallow, lard, cottonseed oil, soybean oil, olein (olive oil),
castor oil (giving the triacetate). The following compds. were also prepd. (nD 30 and oxirane oxygen (%) are given):
benzyl epoxystearate (II), 1.4825, 3.68; Bu epoxystearate, 1.4483, 3.99; 2-chloroethyl epoxystearate ..., 3.83; cyclohexyl
epoxystearate (III), 1.4607, 3.75; dihydronopyl epoxystearate, 1.4728, 3.06; 2-ethylbutyl epoxystearate (IV), 1.4519, 3.56;
2-ethylhexyl epoxystearate, 1.4524, 3.31; methoxyethyl epoxystearate (V), 1.4500, 3.91; isodecyl epoxystearate, 1.4528,
3.19; isoöctyl epoxystearate, 1.4520, 3.39; octyl epoxystearate, 1.4520, 3.30; epoxyoctadecyl epoxystearate (m. 44-6°),
1.4590 (50°), 5.28; tridecyl epoxystearate, 1.4556, 2.90; tetrahydrofurfuryl epoxystearate (VI), 1.4588, 3.77; Ph
epoxystearate (VII), 1.4812, 3.78; acetoxyethyl epoxystearate (VIII), 1.4517, 3.73; Bu epoxytallate, 1.4532, 4.62; glycidol
epoxystearate (IX) (m. 43-4°), 1.4500 (50°), 8.0; sorbitan triepoxystearate, 1.4723, 3.89; polyoxyethylene sorbitan
triepoxystearate, 1.4672, 1.81; epoxidized glycerol monoricinoleate triacetate, 1.4680, 2.53; tert-butylphenyl
epoxystearate, 1.4822, 3.93. Efficient plasticizers of low volatility and migration loss were obtained. Outstanding
compds. with respect to low-temp. characteristics and efficiency were: II, epoxidized Bu esters of tall oil, III, IV, V, VI, VII,
VIII, and IX. 30 references.
~4 Citings
188. Effect of bond structure on the Baker-Venkataraman transformation of acetylanisoyloxyindans and

benzoyloxytetrahydroacetonaphthones
By O'Farrell, M. P.; Wheeler, D. M. S.; Wheeler, M. M.; Wheeler, T. S.
DOI:10.1039/JR9550003986
cf. C.A. 44, 6841b. Confirmation of earlier results (loc. cit.) suggesting that the 5,6-bond in indan derivs. is of a lower
order than the 4,5-bond was obtained by the application of the Baker-Venkataraman transformation (Ia) to 5-acetyl-6- (I)
and 4-acetyl-5-p-anisoyloxyindan (II). 5-Acetyl-6- and 4-acetyl-5-hydroxyindan, prepd. according to Baker (C.A. 31,
3907.1), with p-MeOC6H4COCl in C5H5N yielded I, m. 128-9°, and II, m. 81-3°, resp. Shaking 0.5 g. I and II, resp., in 5
mL. C5H5N with 0.5 g. powd. KOH and acidifying the mixt. yielded 0.3 g. 5-p-anisoylacetyl-6-hydroxyindan (III), yellow
needles, m. 142-3°, and the 5-HO isomer (IV), orange crystals, m. 114-15°, resp. The reaction with I began immediately
and was complete after 20 min., whereas with II it began only after 20 min. and was complete only after several hrs. III
and IV (0.2 g.), resp., in 2 mL. glacial AcOH, boiled 1 min. with a few drops concd. HCl, and hot H2O added until pptn.
began gave 4'-methoxy-6,7- (V), m. 198-9°, and 4'-methoxy-5,6-cyclopentenoflavone, m. 176-7°, resp., showing blue
fluorescence in concd. H2SO4. V was prepd. also according to Lynch, et al. (C.A. 47, 1086i), by heating 0.2 g. I 30 min.
in 2 mL. glycerol at 250° under N and pouring the hot mixt. into 20 mL. H2O. Extension of the I to the 2,3- (VI), 1,2- (VII),
and 2,1-Ac(BzO) (VIII), and 1,3,2-Ac2(BzO) (IX) derivs. of 5,6,7,8-tetrahydronaphthalene (X) supports the view that the
2,3-bond in X is of a lower order than the 1,2-bond, similarly to the indan derivs., since the rates of the transformations
decreased in the order IX, VI, VII, VIII (cf. Berthier and Pullman, C.A. 44, 6395g). The 2,1-Ac(HO) deriv. (XI) of X was
prepd. according to Sergievskaya and Morozovskaya (C.A. 40, 7186.5). Heating 116 g. 2-AcO deriv. of X 1.75 h. at 120°
with 116 g. AlCl3 and decompg. the product by ice and HCl yielded 64 g. 2,3-Ac(HO) deriv. (XII) of X, m. 72-3°, confirmed
by dehydrogenation (Pd-C) 2 h. at 270-300° in CO2 to 2,3-AcC10H6OH, m. 111-13°. Acetylation of 25 g. XII by Ac2O-
AcONa gave its acetate (XIII) (24.5 g.), m. 55-7°, rearranged by heating 6 h. with AlCl3 at 75-80° to the 1,3,2-Ac2(HO)
deriv. (XIV) of X (1.5 g. from 7.5 g. XIII), m. 128-30°. Methylation by K2CO3-Me2SO4-Me2CO of the 1,2-Br(HO) deriv. of
X, or bromination of the 2-MeO deriv. of X gave the 1,2-Br(MeO) deriv. (XV) of X. Dropwise addn. during 20 min. of 5.5
mL. MeCN in 25 mL. ether to a boiling Grignard soln. of 32.7 g. XV in 170 mL. ether with 4.9 g. Mg and traces of iodine
and EtBr yielded, after refluxing 2 h., standing 1 day, and the usual decompn. and extn., 2.2 g. 1,2-Ac(MeO) deriv. (XVI)
of X, m. 81-2°, also prepd. (1.8 g.) (for comfirmation by mixed m.p.) by adding 5.4 g. CdCl2 to the cold Grignard soln. of
12 g. XV, 60 mL. ether, 1.6 g. Mg, traces of iodine and EtBr, refluxing 2-5 h. and again 1.5 h. with 0.5 g. addnl. CdCl2,
replacing the ether by C6H6, adjusting the vol. to 50-60 mL. (Cason, C.A. 41, 397g), adding dropwise to the stirred boiling
Cd aryl soln. 4 mL. AcCl in 60 mL. C6H6, refluxing 8 h., and pouring the mixt. onto ice and dil. H2SO4. Demethylation of
XVI to the 1,2-Ac(HO) deriv. (XVII) of X, m. 112-13°, was done by refluxing with AlCl3 in C6H6 in the usual way, and
remethylation of XVII by K2CO3-Me2SO4-Me2CO gave the expected XVI, indicating no rearrangement. Heating 0.5 g.
XVI, however, with 2.5 g. AlCl3 in 0.5 g. fused NaCl (Bruce, et al., C.A. 48, 12055f) 3 min. at 170-90°, followed by the
usual decompn. and extn. gave XII, thus involving either migration of the Ac group or rearrangement of the reduced ring.
A 3rd attempted demethylation by keeping 1.4 g. XVI, 12 mL. Ac2O, and 12 mL. 55% HI 2 days at 45° and pouring the
product into satd. aq. NaHSO3 yielded 0.4 g. 5,6,7,8-tetrahydro-2-naphthol (XVIII), m. and mixed m.p. 59-62°, thus
involving an acid-catalyzed deacylation (Schubert and Latourette, C.A. 48, 639h). Such rearrangement and deacylation
suggest that the Ac group in XVII is sterically hindered (cf. van Helden, et al., C.A. 49, 3863a). The UV absorption
spectra of XII and XVII confirm such steric inhibition of conjugation between CO and the arom. ring in XVII. BzCl and
C5H5N with XI, XII, XVII, and XIV gave the corresponding benzoates: rhombs, m. 102-4°; plates, m. 81-2°; needles, m.
62-3°; and rhombs, m. 116-17°, resp. The results of the Ia of these benzoates were (positions of the BzCH2CO and OH
groups in X, color of crystals, m.p., color in alc. FeCl3, duration of reaction, % yield given): 2, 1, orange, 117-19°, green,
180-240 min., 80; 3, 2, yellow-orange, 107-8°, brown, 30-60 min., 89; 1, 2 [mixed with 5,6-cyclohexenoflavone (XIX)], -, -,
red-brown, 120-80 min., 83; (3, 2, and 1-Ac) mixed with (1,2, and 3-Ac) (sepd. by cold ether), orange and yellow, resp.,
166-8° and 118-19°, resp., brown and red, resp., 15-60 min., 90. Cyclization of the preceding benzoylacetyl-5,6,7,8-
tetrahydronaphthols by the method used with III and IV gave the following cyclohexenoflavones (fluorescence color in
concd. H2SO4 given in parentheses): 7,8 (XX), m. 194-5°, (blue-green); 6,7 (XXI), m. 170-1°, (blue); XIX, m. 130-1°,
(green); 8-Ac-6,7 (XXII), m. 188-90°, (blue); 8-Ac-5,6 (XXIII), m. 175-7°, (green). A possible steric effect in the Ia of the
benzoate of XVII is discussed with the help of mol. models, and it is concluded that any hindrance to rotation of the Ac
group may be ignored in the Ia. The structure of XXII was confirmed by refluxing 5 h. with 85% H3PO4 (Arnold and
Rondestvedt, C.A. 41, 954f), and pouring the mixt. into H2O to give XXI, m. and mixed m.p. 169-71°. The structures of
XIX-XXIII were further confirmed by their UV absorption spectra, recorded with those of XII, XVII, and XVIII. It is stressed
that conclusions reached on the effect of bond structure on the Ia and the relative order of the 1,2- and 2,3-bonds apply
strictly only to the compds. studied.
~0 Citings
189. Decomposition of l-tyrosine by tubercle bacilli. The formation of N-acetyltyramine, a new compound from
tyramine, by tubercle bacilli
By Shirai, Yutaka
From Kekkaku (1955), 30, 628-30. Language: Unavailable, Database: CAPLUS
cf. C.A. 49, 7053f. When glycerol in Sauton medium was replaced by glucose, tyrosol (p-hydroxyphenethyl alc.) was no
longer produced, but p-hydroxyphenylacetic acid and an unknown cryst. product with pos. Millon's reaction were isolated.
The latter compd. was identical with monoacetyltyramine obtained by acetylating tyramine (Wünsche, Nauyn-
Schmiedeberg's Arch. exptl. Pathol. Pharmakol. 96, 318(1923)) and hydrolyzing the diacetyl product (Sealock, C.A. 41,
2404h). The new compd. m. 130° and was hydrolyzed with 20% NaOH at room temp. to give free tyramine. Hydrolysis
did not take place with 10% Na2CO3. Schotten-Bauman's benzoylation in carbonate soln. gave O-benzoyl-N-
acetyltyramine. In consequence, the original compd. is N-acetyltyramine. It is concluded that the presence of glucose in
the medium tends to result in formation of the acetic acid deriv., while the presence of glycerol results in formation of the
alc. deriv. The mechanism of acetylation of tyramine may involve catalysis by acetyl coenzyme A as in the case of
acetylation of sulfanilamide or histamine.
~3 Citings
190. Chemistry of fungi. XXV. Oöisporein, a metabolite of Chaetomium aureum

By Lloyd, G.; Robertson, Alexander; Sankey, G. B.; Whalley, W. B.
DOI:10.1039/jr9550002163
cf. C.A. 49, 15844c. Oösporein (I) was isolated from a strain of C. aureum and some derivs. prepd. The mold was
grown at 25° for 21 days on a modified Saunders medium contg. (all amts. per l.) 50 g. glucose, 2 g. KH2PO4, 0.5 g.
CaCl2, 1.4 g. malt ext., 0.3 g. (NH4)2SO4, 0.25 g. MgSO4, 0.5 g. H3BO3, 0.25 g. FeCl3, 0.5 g. TlCl, 0.05 g. KI, 0.05 g.
CuSO4, 0.5 g. MnCl2, and 0.5 g. ZnSO4. The mycelium was collected, dried, powd., and exhaustively extd. (Soxhlet) 4
days with petr. ether (b. 40-60°) and then with Et2O. The metabolic liq. was concd. in vacuo to about 1/10 its vol.;
several days later the ppt. (about 10 g. from 180 l. fluid) was collected, dried, repeatedly extd. with 1 l. boiling Me2CO,
and the ext. concd. to about 30 mL.; I then sepd. The combined yield of I varied from 0.03 to 0.11 g. per l. of culture fluid.
The relative distribution between liq. and mycelium also varied widely. Growth of the mold at 30° did not appear to alter
the yield of I but at 15-16° the yield was considerably lower; when the glucose was replaced by glycerol, the organism did
not produce the pigment. I, bronze-colored plates, m. 260-75° (decompn.) (from Me2CO-petr. ether); tetraacetate, yellow
plates, m. 191° (from EtOAc-petr. ether), mixed m.p. with authentic material not depressed and IR absorption spectra
identical; tetrahydroöcta-O-acetyloösporein, m. 250° (from EtOH), the IR absorption spectrum being identical with
authentic material. Ethereal CH2N2 rapidly added to 1 g. I in 175 mL. cold MeOH, after 5 min. the mixt. acidified with 2N
H2SO4, concd. in vacuo to about 20 mL., 50 mL. water added, the ppt. purified from petr. ether, and then by chromatog.
on Al2O3 gave tetra-O-methyloösporein (II), orange needles, m. 125°, sol. in the common org. solvents, insol. in 2N
Na2CO3, and giving a neg. ferric reaction. With less CH2N2, methylation of I gave 2 isomeric tri-O-Me ethers (III and IV):
III, golden plates, m. 154° (from aq. MeOH); IV, yellow plates, m. 192° (from aq. MeOH), mixed m.p. with III 130-42°. III
and IV gave blood-red ferric reactions in EtOH and formed deep purple solns. in 2N NaHCO3 from which they were
recovered unchanged on acidification. Treatment of III and IV with excess CH2N2 gave II quant. II (3 g.) in 150 mL.
MeOH hydrogenated 30 min. with a Pd-C catalyst, the solvent removed in vacuo, and the residue recrystd. from aq.
MeOH gave 2.2 g. tetrahydro deriv. (V), needles, m. 197°, sol. in 2N NaOH and giving a neg. ferric reaction. V was also
obtained by redn. of II in MeOH in SO2. Acetylation of 0.2 g. III with 5 mL. Ac2O and H2SO4 on the steam bath for 15
min. afforded the tetra-O-acetyl deriv., needles, m. 146° (from aq. AcOH), identical with the product obtained by reductive
acetylation of II, insol. in 2N NaOH and giving a neg. ferric reaction. III (1 g.) methylated by either Me2SO4 or MeI-
K2CO3-Me2CO 6 h. invariably gave 0.8 g. mixt., m. 130-40°, which was sepd. by fractional crystn. from MeOH into
1,2,4,6,8,9-hexamethoxy-3,7-dimethyldibenzofuran (VI), plates, m. 141-2°, and tetrahydroöcta-O-methyloösporein,
octahedra, m. 179°, both products giving neg. ferric reactions and were insol. in 2N NaOH. Demethylation of 0.5 g. VI
with a boiling mixt. of 10 mL. HI (d. 1.7) and AcOH (from 5 mL. of the anhydride) 10 min. and diln. with water afforded
1,2,4,6,8,9-hexahydroxy-3,7-dimethyldibenzofuran (VII), needles, m. 300° (decompn.) (from MeOH), which oxidized
rapidly on exposure to air. Acetylation of VII gave the hexaacetate, prisms, m. 274° (from MeOH). Methylation of VII
regenerated VI, m. and mixed m.p. 141-2°.
~1 Citing
191. Anomerization of acetylated alkyl glucopyranosides

By Lemieux, R. U.; Shyluk, W. P.
DOI:10.1139/v55-015
An intramol. mechanism based on ion-pair intermediates is postulated for the anomerization of acetylated alkyl
glucopyranosides. Me β-D-glucopyranoside tetraacetate (labeled) in the MeO group with C14 and possessing a
radioactivity of 98,000 c.p.m., counted as BaCO3 at infinite thickness), m. 104.5-5.0°, and nonradioactive Me β-L-
glucopyranoside tetraacetate were anomerized with BCl3 in CHCl3 at room temp. for 24 h. Sepn. and isolation in the
usual manner (cf. Lindberg, C.A. 43, 3795d) yielded Me α-D-glucopyranoside tetraacetate, m. 101.5-2.5°, with a
radioactivity of 3560 c.p.m. (theor. radioactivity 3860 c.p.m. based on intermol. mechanism and quant. yield) and Me α-L-
glucopyranoside tetraacetate, m. 102-2.5°, and having an insignificant radioactivity of 6 c.p.m. An attempt to anomerize
Ph β-D- and Ph α-D-glucopyranoside tetraacetates yielded mainly the starting material. These exptl. facts show that
both anomerization and glycosidic cleavage result from an attack by the acid catalyst at the aglycon group. When the
aglycon group is an alkylate, where charge localization is high, the interaction can reasonably be expected to lead to a
stable ion-pair structure which can collapse to the α-glycoside. It is reasonable that ion sepn. leading to glycosidic
cleavage should be extensive when the anion of the ion-pair can dissipate the neg. charge through resonance as in the
case of the phenolate ion.
~9 Citings
192. A general method for the acetylation of hydroxy fatty acids and their glycerides
By Pathak, K. D.; Aggarwal, J. S.
From Journal of Scientific & Industrial Research (1955), 14B, 637-9. Language: Unavailable, Database: CAPLUS
At 27-32°, acetyl chloride in ether soln. quantitatively acetylates unsatd. hydroxy fatty acids having conjugated double
bonds. If the fat is highly polymerizable, acetylation must be carried out at 0-5°. The method was used with castor oil,
ricinoleic acid, kamalaseed oil, α- and β-kamololenic acids, 12-mono-and 9,10-dihydroxystearic acids.
~0 Citings
193. ω-Hydrazino-γ-picolinic acid hydrochloride

By Takeda, Tokuharu; Maejima, Yoshiko; Yukuye, Hisashi
From No Corporate Source data available (1955), JP 30006117 B 19550800, Language: Unavailable, Database:
CAPLUS
31. Isonicotinoyl hydrazide (19.6 g.) in 124 cc. pyridine is treated with 26 g. PhSO2Cl, kept 1 hr., the pyridine evapd. in
vacuo, poured into large amt. of H2O, and recrystd. from alc. to yield 1-isonicotinyl-2-benzenesulfonyl hydrazine (I). I (16
g.), 9.6 g. Na2CO3, and 5.8 g. thiosemicarbazide in 51.2 cc. glycerine is heated at 160° 2 min., 64 cc. H2O added, and
cooled to yield isonicotinaldehyde thiosemicarbazone (II), m. 220° (decompn.). II (19 g.), 57 cc. 80% hydrazine hydrate,
and 1 g. Pb oxide is refluxed 2.5 hrs., condensed in vacuo, MeOH added, the pptd. mass removed, the remaining oily
substance acetylated with 4 vols. Ac2O, and the ppt. washed with Ac2O and recrystd. from EtOAc to yield γ-
pyridinealdehyde acetylhydrazone (III), m. 139.5°. The catalytic reduction is carried out with III (6 g.), 3 g. 5:95 Pd-
BaSO4, and EtOH, condensed in vacuo, hydrolyzed with 10% HCl 30 min., condensed in vacuo, and recrystd. from EtOH
to yield 3 g. ω-hydrazino-γ-picolinic acid hydrochloride, hydroscopic. This compd. has antituberculous activity.
~0 Citings
194. The biosynthesis of chloramphenicol. II. Acetylation of p-nitrophenylserinol

By Gottlieb, David; Robbins, P. W.; Carter, H. E.
From Journal of Bacteriology (1956), 72, 153-6. Language: Unavailable, Database: CAPLUS
cf. C.A. 48, 12897i. p-Nitrophenylserinol, a hydrolysis product of chloramphenicol, stimulates antibiotic production by
Streptomyces venezuelae in a synthetic glycerol-lactate medium. Most of this stimulation results from the formation of N-
(acetyl)nitrophenylserinol, which is itself an antibiotic. It is apparent that large amts. of a less active analog stimulate the
formation of an active antibiotic. Hence, an increase in the biol. activity sometimes observed when different compds. are
added to cultures need not be due to their activity as precursors, even if the structure of the stimulatory material is closely
related to the structure of a portion of the complete mol.
~3 Citings

195. The acetylation of organic hydroxy compounds with ketene
By Dunbar, Ralph E.; Bolstad, Luther L.
DOI:10.1021/jo01115a613
cf. C.A. 33, 21098. Ketene, prepd. by the pyrolysis of Me2CO, has been used to acetylate (CH2OH)2, MeCHOHCH2OH,
(HOCH2CH2)2O (I), (HOCH2CH2OCH2)2 (II), MeOCH2CH2OH (III), EtOCH2CH2OH (IV), BuOCH2CH2OH (V), glycerol
(VI), sorbitol, mannitol, and D-glucose in the presence of traces of concd. H2SO4. CCl4, not previously reported, was
found to be a suitable solvent for the solid, polyhydroxy compds. The several liquid acetates were purified by treatment
with anhyd. Na2CO3 and vacuum distn. The 2-hydroxy groups in each of the glycols were acetylated, and VI produced
the triacetate. The ether linkage in I, II, III, IV, and V was not ruptured with ketene under the exptl. conditions. The
sorbitol, mannitol, and D-glucose were each completely acetylated in boiling CCl4. After completion of the acetylation,
the CCl4 soln. was shaken with dil. Na2CO3 soln., washed twice with H2O, solvent removed by heating on steam-bath,
H2O added to the brown oily residue, remaining CCl4 removed by boiling, EtOH added to dissolve product while the soln.
was hot, treated with Norit, filtered hot, and allowed to crystallize. If necessary the product was recrystd. from H2O-EtOH
with a 2nd treatment with Norit, and dried over P2O5 in a vacuum desiccator. Acetylation of D-glucose in CCl4 was found
to be far superior to the acetylation in Me2CO.
~1 Citing
196. Steroid total synthesis-hydrochrysene approach. V. Introduction of oxygen at the 11-position

By Johnson, Wm. S.; Kemp, A. D.; Pappo, Raphael; Ackerman, James; Jones, Wm. F.
DOI:10.1021/ja01605a018
trans-anti-trans-1-Methoxy-8β-acetoxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (I) (0.404 g.),
m. 149-50°, 0.668 g. Pb(OAc)4, and 1 cc. glacial AcOH heated 20 min. on the steam bath with stirring, cooled, treated
with glycerol and 1 cc. H2O, and filtered, and the residue washed with H20 gave 96% crude 12-acetoxy deriv. (II) of I,
which chromatographed on Al2O2 and recrystd. from 95% EtOH contg. a few drops of C6H6 gave pure II, plates, m.
205.5-11.7° with slight decompn. and previous softening. I (3.40 g.), m. 148-9°, 5.52 g. Pb(OAc)4, and 8.3 cc. glacial
AcOH heated 27 min. under N with stirring on the steam bath, the mixt. treated with 2 drops of glycerol and 8 cc. H2O,
the crude product filtered off and heated 14 hrs. under N at 90-100° with 60 cc. glacial AcOH, the solvent evapd., and the
pale brown residue recrystd. from 75 cc. 95% EtOH and sublimed yielded 2.26 g. 4b,5,6,6a,7,8,9,10,10a,10b-
decahydrochrysene analog (III) of II, rods, m. 157.2-59°; the mother liquor from the 1st crystn. from EtOH evapd. and the
residue chromatographed on Al2O3 yielded 0.07 g. I and 0.247 g. 1:1 mixt. of I and III, m. 131-3°. III (0.011 g.), m. 155.5-
6.5°, in 10 cc. EtOAc hydrogenated 5 min. over 10% Pd-C at atm. pressure and room temp., filtered, and evapd. gave
0.009 g. I. III (0.340 g.), m. 150.5-52° and 0.61 g. BzOH in 5 cc. CHCl3 treated with 1 cc. 0.652M BzO2H in CHCl3 slowly
with stirring at -13° during 13 min., the mixt. stirred 5 hrs. at -3° to -1°, treated with an addnl. 0.3 cc. BzO2H soln. at -3°
during 25 min., refrigerated at 1° overnight, treated again during 20 min. at -3° with 0.245 cc. BzO2H soln., kept 24 hrs. at
1°, washed, dried, and evapd., a 0.211-g. sample of the crude residue (0.435 g.) heated 1 hr. at 235° and about 150
mm., the distillate washed back with Et2O, the Et2O evapd., the BzOH (0.024 g.) distd., the residue distd. at 168-80° and
0.06 mm. for 14 hrs., and the resulting colorless oil crystd. from about 6 cc. MeOH gave 0.080 g. 11-oxo deriv. (IV) of I,
needles, m. 163.5-65°. IV in NaOMe in MeOH shaken in air slowly developed a deep yellow color which changed to blue
upon addn. of concd. HCl. III (0.056 g.), m. 150-2°, in 1 cc. CH2Cl2 treated rapidly with 2.1 cc. 0.66M o-HO2CC6H4CO3H
(V) in Et2O at 10°, the mixt. kept 28 hrs. at 10° and evapd. in vacuo, and the residue pyrolyzed gave at 105-10° and 0.08
mm. during 3 hrs. 0.054 g. forerun and then during 3 hrs. at 125-225° and 0.08 mm. 0.046 g. distillate which crystd. from
MeOH yielded 0.010 g. crude IV, m. 155-60.5°. Neutral fraction (0.039 g.) from the V oxidation heated 9 hrs. at 100° with
10 cc. AcOH and evapd., and the residue chromatographed on Al2O3 gave 0.004 g. 11-OH deriv. (VI) of II, m. 250-5°
(decompn.) (from BuOAc). III (0.116 g.), m. 150-2°, treated 22 hrs. at 10-12° with V, the resulting crude product heated 6
hrs. under N with 10 cc. AcOH contg. 10 drops of H2O and evapd. in vacuo, and 0.076 g. of the crude residue (0.152 g.)
chromatographed on Al2O3 yielded 0.029 g. VI, m. 260-8° (decompn.) (from BuOAc). VI (0.076 g.), m. 260-8°, in 10 cc.
4% KOH in MeOH refluxed 2 hrs. under N, the MeOH removed in vacuo, the residual mixt. dild. with H2O and extd. with
BuOAc and C6H6, the combined exts. washed, dried, and evapd., and the residue crystd. from CHCl3-C6H6 gave 0.022
g. trans-anti-trans-1-methoxy-8β,11β,-12α-trihydroxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-
dodecahydrochrysene (VII), m. 206-7°. VII (0.022 g.), m. 206-7° 2.5 cc. glacial AcOH, 0.08 cc. 60% HClO4, and 0.01 g.
30% Pd-C hydrogenated 24 hrs. at 26° and atm. pressure, the mixt. filtered, the filtrate treated with KOAc and filtered, the
filtrate evapd. at 90° and 30 mm., the colorless residue treated with dil. aq. KOH and extd. with Et2O, and the ext.
washed with H2O, dried azeotropically with C6H6, and evapd. yielded 0.0031 g. trans-anti-trans-1-methoxy-8β,-11β-
diacetoxy- 10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (VIII), needles, m. 197.5-99° (from 95%
EtOH), also obtained in 3% yield by chromatography of the hydrogenolysis product of the V oxidation product. VIII
sapond. with dil. NaOH in MeOH yielded the 8β,11β-diol (IX), m. 240-2°. III (1.166 g.), m. 151.5-7.5°, in 20 cc. 100%
HCO2H treated with stirring at 17-22° with 0.41 cc. 30% H2O2, the mixt. stirred about 4.3 hrs. and evapd. at. 20-30° in
vacuo, the gummy residue dissolved in C6H6-Et2O, the soln. washed and worked up, the gummy residue dissolved in 30
cc. abs. EtOH, the soln. poured into 300 cc. liquid NH3, the mixt. treated with stirring with 8.4 g. Na in 7 portions during 1
hr., the NH3 evapd., the remaining NH3 codistd. with Et2O, the residue treated with cold H2O and Et2O, the aq. layer
extd. with Et2O, the combined Et2O solns. worked up, and the gummy residue boiled with 4 cc. EtAc and cooled,
deposited 0.338 g. IX, microprisms, m. 240-1°; the gummy residue (0.533 g.) from the mother liquor chromatographed on
35 g. Florisil gave 0.253 g. 8β-OH analog (X) of I, m. 149-54°, 0.120 g. 11αepimer (XI) of VIII, m. 149-54°, resolidified
and remelted at 180° and 0.063 g. IX, m. 236-40°. IX treated with CH2:CMeOAc (XII) and p-MeC6H4SO3H (XIII) in the
usual manner gave VIII, m. 185-8° (from 95% EtOH). 8β-OH Analog (XIV) of IV (0.329 g.), m. 181.4-2.6°, in 25 cc.
tetrahydrofuran added slowly during 1.75 hrs. to 0.396 g. LiAlH4 in 25 cc. tetrahydrofuran, the mixt. refluxed 2 hrs. under
N, and treated with 5 cc. EtOAc and 50 cc. 2N H2SO4, the aq. layer extd. with Et2O, the combined org. layers washed
with H2O, neutralized, dild. with 10 cc. EtOH, and evapd. in vacuo, and the residual yellow solid chromatographed on 15
g. Florisil yielded 0.0312 g. IX, m. 241-3° which acetylated gave VIII, m. 193-7°; further elution gave 0.274 g. XI, needles,
m. 179.5-83° (from EtOAc), m. 183-3.9° (from another run) [XI diacetate, needles, m. 179.5-80.7° (from MeOH)]. OsO4
(0.075 g.) and 5 drops of pyridine in 1.5 cc. dry CH2Cl2 added to 0.047 g. III, m. 152-7° in 3 cc. CH2Cl2, the mixt. kept 6
days at room temp. and evapd., the residue treated with 5 cc. H2O, 7 cc. abs. EtOH, 1 cc. C6H6, and 1 g. NaHSO3,
refluxed 4 hrs., and filtered, the black residue extd. with abs. EtOH, the combined filtrate and ext. evapd. to dryness in
vacuo, the residue dissolved in BuOAc, washed neutral, and evapd., and the glassy residue, probably a mixt. of the 8β-
acetate (XlVa) of the 12β-epimer (XV) of VII and the free tri-OH compd.; XIVa m. 211.5-14.5° (from abs. EtOH). III
(0.340 g.), 50 cc. dry Et2O, and 0.250 g. OsO4, kept 2 days at room temp., the dark mixt. evapd. to dryness in a stream
of N, the residue dissolved in 10 cc. abs. EtOH and poured into 100 cc. liquid NH3 the mixt. treated during 0.5 hr. with 2.8
g. Li, and the crude product isolated in the usual manner and crystd. from EtAc gave 0.050 g. XV, m. 238-40°. trans-anti-
cis-1-Methoxy-8β-acetoxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (XVI) (1,05 g.), m. 130-
2°, and 2,10 g. Pb(OAc4) in 1.0 cc. AcOH heated 35 min. with occasional swirling on the steam bath, the mixt. treated
with a few drops of glycerol, and dild. with H2O and Et2O, the aq. layer extd. with Et2O, and the combined org. layer and
ext. worked up yielded 0.670 g. 12-AcO deriv. (XVII) of XVI, prisms, m. 179-84° (decompn.), 187-9° (decompn.)
(vacuum); 2nd crop, 0.670 g. XVI (0.200 g.), m. 132-4°, treated with 0.400 g. Pb(OAc)4 in 0.5 cc. AcOH and the crude
product chromatographed on 10 g. Florisil gave 0.036 g. unchanged XVI and 0.156 g. XVII, m. 155-68°. XVII (0.748 g.)
in 10 cc. AcOH heated 2 hrs. at 120° and evapd. in an air stream of the steam bath gave 0.520 g. trans-syn-cis-isomer
(XVIII) of III, needles, m. 143.5-4.5° (from 95% EtOH) (2nd crop, 0.047 g.); occasionally a polymorphic form, m. 120-1 °
resolidified and remelted at 137-40° was obtained. XVII (0.156 g.) heated 2 hrs. in 3 cc. AcOH at 120° yielded 0.083 g.
XVIII, m. 139-43°. XVIII (0.200 g.), m. 139-42°, in 2 cc. CHCl3 treated with 1.4 cc. 0.45M BzO2H in C6H6, the mixt. kept
25 hrs. at 0° dild. with Et2O, and worked up, and the oily residue (0.26 g.) chromatographed on 12 g. Florisil gave 0.009
g. XVIII and 0.087 g. 12-BzO analog (XIX) of XVII, plates, m. 198-200° (from 95% EtOH); further elution of the column
gave 0.036 g. oil, presumably impure stereoisomeric acetate benzoate of XVII, which was combined with the oily residue
from the recrystn. mother liquors of XIX. Elution with iso-PrOH gave 0.062 g. trans-syn-cis-1-methoxy-8β-acetoxy-10a-
methyl-11,12-dihydroxy-4b,5,6,6a,7,8,9,-10,10a,10b,11,12-dodecahydrochrysene (XX), prisms, m. 170-2° (from ligroine).
III (0.600 g.), m. 138-40°, in 8 cc. C6H6 and 5.0 cc. 0.39M BzO2H in C6H6 kept 60 hrs. at 0° and the crude oily product
dissolved in 95% EtOH and seeded deposited 0.207 g. XIX, m. 198-200°. Oily benzoate fraction (0.040 g.) from the
BzO2H oxidation kept 1 day at room temp. in 3 cc. MeOH and 10 cc. concd. HCl, the blue soln. treated with excess solid
NaHCO3, H2O, and Et2O, the aq. layer extd., the combined Et2O solns. worked up, and the yellow oily residue
chromatographed on 2.5 g. Florisil yielded 0.017 g.X. X with Ac2O-pyridine yielded 80% IV, m. 166-8° (from MeOH), also
obtained by pyrolysis of XIX in 14% yield. XIX (0.200 g.), m. 198-200° in 25 cc. MeOH kept 60 hrs. at room temp. with 25
cc. concd. HCl gave 0.059 g. X, m. 181-3° (2nd crop, 0.012 g.). XVIII (0.600 g.), m. 137-40°, 8 cc. CHCl3, and 6.0 cc.
0.311M BzO2H in CHCl3 kept 48 hrs. at 0° and evapd. in an air stream, the residue dissolved in 25 cc. MeOH, treated
slowly during 15 min. with 25 cc. concd. HCl, and kept 6 days at room temp., and the black soln. worked up in the usual
manner yielded 0.628 g. crude brown product which chromatographed on 15 g. Florisil gave 52% X. XX (0.016 g.), m.
170-2°, in 2 cc. MeOH treated 22 hrs. at room temp. with 10 cc. concd. HCl, the mixt. worked up in the usual manner,
and the crude product chromatographed on 1 g. Florisil yielded 0.00 t g. X, m. 180-2° (from 95% EtOH). cis-1-Methoxy-
8α-hydroxy-10a-methyl-5,6,6a,7,8,9,10,10a, 11, 12- decahydrochrysene (XXI) (30.50 g.), m. 157-9° in 100 cc. dry
tetrahydrofuran treated with 450 cc. dry Et2O and 11. liquid NH3, the mixt. treated with stirring during 5 min. with 36 g. K,
stirred 20 min., and treated dropwise during 20 min. with 90 cc. abs. EtOH in 70 cc. dry Et2O, the NH3 evapd., the
residue treated with C6H6 and ice water, the aq. layer extd. with C6H6, and the combined C6H6 solns. worked up gave
23.11 g. cis-anti-trans-1-methoxy-8α-hydroxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (XXII),
m. 154-7° (2nd crop, 1.67 g.). XXII acetate (XXIII), m. 113-15°, in 1.5 cc. AcOH treated at 105° with 2.93 g. Pb(OAc)4,
cooled, dild. with H2O, and extd. with Et2O, the ext. worked up, and the oily residue chromatographed on 80 g. Florisil
yielded 0.305 g. unchanged XXIII, m. 104-10°, and 1.225 g. 12-AcO deriv. (XXIV) of XXIII, prisms, m. 164-6° (from Et2O-
ligroine, b. 65-8°). XXIV (1.12 g.), m. 140-55° in 20 cc. AcOH refluxed 16 hrs. under N, concd., and dild. with MeOH
yielded 0.860 g. cis-anti-trans-isomer (XXV) of III, rods, m. 145-6° (from abs. EtOH). Crude XXIII (20.00 g.), m. 111-14°,
in 50 cc. glacial AcOH treated at 95° with 34.0 g. Pb(OAc)4 with vigorous stirring during 5 min., the mixt. dild. after 10
min. with C6H6, the soln. worked up, the oily residue heated 17 hrs. under N in 300 cc. glacial AcOH, and the mixt.
concd. to 80 cc. and cooled deposited 13.89 g. XXV, m. 143-5° (2nd crop, m. 134-40°). XXV (0.835 g.), m. 143-6° in 10
cc. C6H6 treated at 5° with 14 cc. 0.209M BzO2H, the mixt. kept 24 hrs. at 5°, treated with 0.7 g. BzOH. kept 24 hrs. at
5°, the resulting crude amorphous product (1.11 g.) dissolved in 18 cc. abs. EtOH, the soln. added to 1 g. Li in 350 cc.
liquid NH3, the mixt. treated during 0.5 hr. with an addnl. 1.8 g. Li and worked up in the usual manner, and the resulting
crude, oily product (0.700 g.) triturated with Et2O gave 0.170 g. cis-anti-trans-isomer (XXVI) of the 8α-epimer of IX,
plates, m. 192-3° (from Me2CO); the combined residues from the crystn. and trituration (0.530 g.) chromatographed on
20 g. Forisil gave 0.130 g. cis-anti-trans-1-methoxy-8α-12-dihydroxy-10a-methyl-4b,5,6,6a,7,8,9,10,1Oa,1Ob,11,12-
dodecahydrochrysene (XXVII), m. 153-8°, and 0.235 g. crude 11β-OH isomer of XXVII, m. 189-91° (from Me2CO); further
elution gave 0.090 g. crude product which recrystd. from Me2CO yielded 0.070 g. 11α-epimer of XXVI, colorless rods, m.
220-1°. XXII (1 g.), m. 124-6°, in 20 cc. pyridine and 10 cc. Ac2O heated 10 min. on the steam bath, cooled, poured into
ice and aq. NaHCO3, and extd. with Et2O, the ext. worked up, the residue chromatographed on 40 g. Florisil, the
resulting oily acetate (1.02 g.) dissolved in 1 cc. AcOH, the soln. treated on the steam bath with 2 g. Pb(OAc)4, the mixt.
heated 35 min., treated with a few drops of glycerol, cooled, dild. with H2O, and extd. with Et2O, the ext. worked up, and
the pale yellow oily residue chromatographed on 40 g. Florisil gave 0.175 g. oily XXII, 0.150 g. cis-syn-cis-1-methoxy-8α-
acetoxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b-decahydrochrysene (XXVIII), prisms, m. 112-14° (in some runs a
polymorphic modification, m. 143-3.5°, was obtained) (from Me2CO), and 0.365 g. cis-syn-cis-1-methoxy-8α,12-
diacetoxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (XXIX), platelets, m. 128-31° (decompn.)
(from petr. ether). XXIX (0.100 g.) in 2 cc. AcOH heated 70 min. at 110° gave 0.077 g. XXVIII, prisms, m. 143-3.5° (from
MeOH). Crude oily product (14.4 g.) contg. XXII (obtained by LiAlH4 reduction of the ketone) in 50 cc. pyridine treated at
5° with swirling with 21 g. BzCl, the mixt. heated 15 min. on the steam bath, cooled, treated with 50 cc. pyridine and then
50 cc. H2O, heated 0.5 hr. on the steam bath; dild. with an addnl. 50 cc. H2O, concd. to about 30 cc. in vacuo, and extd.
with Et2O-C6H6, and the combined org. solns. worked up gave 11.35 g. 8α-BzO analog (XXX) of XXIX, prisms, m. 153-4°
(from abs. EtOH); 2nd crop, 0.81 g. XXVIII hydrogenated over PtO2 and the mixt. processed for XXX gave a 68% yield.
Pure XXVIII, m. 124-6°, gave similarly 95% XXX. XXX (0.975 g.), m. 145-52°, in 1 cc. AcOH treated with 1.34 g.
Pb(OAc)4 at 100°, the mixt. worked up after 5 min., and the crude product chromatographed on 40 g. Florisil gave 0.280
g. XXX, m. 145-50°, and 0.345 g. 8α-BzO analog of XXVIII, m. 93-8° (from MeOH). 1-Methoxy-6aα,8β-diacetoxy-10a-
methyl-4b,5,6,6a,7,8,9,-10,10a, 10b,11,12-dodecahydrochrysene (XXXI) (0.395 g.), m. 172-8° 0.590 g. Pb(OAc)4, and 1
cc. glacial AcOH stirred 20 min. at 70° treated with 4 drops (CH2OH)2, cooled, and dild. with H2O and Et2O, the Et2O
layer worked up, the residue (0.428 g.) dissolved in 5 cc. AcOH and heated 6 hrs. on the steam bath, and the product
isolated in the usual manner and chromatographed on 20 g. Florisil yielded 0.175 g. syn-cis-1-methoxy-8β-acetoxy-10a-
methyl-4b,5,7,8,9,10,10a,10b-octahydrochrysene, plates, m. 148-53° (from Et2O-petr. ether), and 0.100 g. trans-syn-cis-
6aα,8β-diacetoxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b-decahydrochrysene, colorless needles, m. 178-83°.
~1 Citing
197. Recent synthetic work in the phospholipide field

By Baylis, R. L.; Bevan, T. H.; Malkin, T.
From Biochem. Problems Lipids, Proc. Intern. Conf., 2nd., Ghent (1956), 91-4. Language: Unavailable, Database:
CAPLUS
Starting with monobenzyl monoglycerides and PhOPOCl2, both lysolecithin and lysokephalin have been prepd.; the
former has unusual surface active properties, giving gelatinous solns. in H2O. By-products, such as triesters, and satd.
rather than the unsatd. acids found in natural products, led to the alternative synthesis of a series of glycol analogs,
resulting in pure products. Glycerol benzyl ether in dry C6H6 contg. dry C5H5N was acetylated by 1 mole acid chloride,
cooled, allowed to stand overnight, the solvents evapd., the residue dissolved in Et2O, washed, dried, and recrystd. from
EtOH, yielding the monoacyl ether: palmityl ether, m. about 25°; stearyl ether m. about 32-33°. The palmityl compd. (8
g.) in dry C5H5N stirred with 4 g. PhOPOCl2 and 1 cc. dry C5H5N, added to 3.7 g. carbobenzoxyethanolamine, left
overnight, and isolated yielded 12.8 g. oil, 2.5 g. of which hydrogenated in glacial AcOH (50:50 Pd black-Adams catalyst),
crystd. several times from EtOH, and extd. with boiling Et2O yielded 0.3 g. lysokephalin, sinters at 90°, decomp. above
235°. Using the method of Baer and Kates (C.A. 44, 1023d) with choline iodide instead of the chloride, from 9.1 g. 3-
palmityl 1-benzyl glyceryl ether was isolated lysolecithin (sinters at 80-90° and decomp. above 240°) after addn. of dry
Et2O to a soln. in dry CHCl3 and keeping over P2O5. Using an earlier method by the authors (C.A. 50, 1583a), an acyl
glycol iodohydrin was refluxed with a dried Ag salt of phenylphosphoryl-N-(carbobenzoxy)ethanolamine 3 hrs., the
solvent removed in vacuo, the residue dissolved in Et2O, washed with NaHCO3 soln., then with H2O, dried, and the
protecting groups removed by hydrogenolysis (Pd black-Adams catalysis), giving good yields of stearoylglycol kephalin,
m. 216-7° (decompn.); palmitoylglycol kephalin, m. 218-19° (decompn.); myristoylglycol kephalin, m. 222-3° (decompn.);
lauroylglycol kephalin, m. 224-5° (decompn.). The method for the prepn. of the Ag is given.
~0 Citings
198. Determination of hydroxyl indexes by acetylation with acetic anhydride

By Hauschild, Remi; Singer, Klaus; Petit, Jean
From Bulletin de la Societe Chimique de France (1956), 768-72. Language: Unavailable, Database: CAPLUS
Details of the method of Meier (C.A. 46, 1775i) with modifications proposed by Pohle and Mehlenbacher (C.A. 41, 4662a)
have been modified to permit the detn. of HO groups of primary and secondary alcs. with satisfactory precision. Purified
Ac2O (above 99%) and redistd. anhyd. pyridine, b740-2 114.5-5.0, nD 25 1.5074, are essential. Heat the sample 1 hr. at
90-100° in 20 ml. Ac2O-pyridine (1:10) in a 300-cc. Erlenmeyer flask connected to a 60-cc. air condenser with ground-
glass joint. Dil. the cooled mixt. with 25 cc. H2O, washing the walls and joints of the app. Titrate the cold hydrolysis mixt.
with N KOH against phenolphthalein. Detns. of the HO index for MeOH, EtOH, BuOH, CH2:CHCH2OH, C6H11OH, o-
MeC6H10OH, p-MeOC6H4CH2OH, HOCH2CH2OH, HOCH2CHOHCH2OH, HOCH2(CHOH)4CH2OH, C(CH2OH)4, and
poly(vinyl alc.) show that a 5-fold excess of Ac2O, a sufficient period of heating, and a temp. 10° below the b.p. of the
sample together with high purity of reagent ensure satisfactory results.
~0 Citings
199. Adrenochrome derivatives. I. Determination of the structure of adrenochrome monosemicarbazone

By Iwao, Junichi
From Pharmaceutical Bulletin (1956), 4, 244-7. Language: Unavailable, Database: CAPLUS,
DOI:10.1248/cpb1953.4.244
cf. C.A. 51, 5288e. Synthetic evidence confirmed the structure of the title compd. as 1-methyl-3-hydroxy-5-
semicarbazono-6-oxo-2,3,5,6-tetrahydroindole (I) (rather than the possible 5-oxo-6-semicarbazono isomer). Catalytic
hydrogenation (Pd-C) of 1 g. I in 70 cc. glacial AcOH at ordinary temp. and pressure yielded 0.6 g. 5,6-
(NH2CONHNH)(HO) deriv. of 1-methylindole (II), m. 205° (decompn.), methylated by Me2SO4 in alk. soln. to the 5,6-
(NH2CONHNH)(MeO) deriv. (III) of II, m. 210° (decompn.). Pyrolysis of 2.3 g. III by heating with 4 g. anhyd. Na2CO3 and
10 cc. glycerol at 185-95° until evolution of N ceased, pouring the mixt. into H2O, extg. with ether, and extg. the residue
from the ether ext. with ligroine yielded 0.4 g. 6-MeO deriv. of II, m. 30° (picrate, m. 123°), λ 224, 275, and 292 mµ (log ε
5.43, 4.68, and 4.74), identical with the product obtained according to Potts and Saxton (C.A. 49, 8908d) by adding 1.8 g.
6-methoxyindole in 10 cc. dry ether gradually to 50 cc. liquid NH3 contg. 0.31 g. Na and a small amt. of Fe(NO3)3, after
10 min. adding 2.1 g. MeI, stirring 15 min. while NH3 evapd., and extg. with ether. The position of the semicarbazone
group in I was thus established. Similar catalytic reduction (Pd-C) of 0.5 g. adrenochrome monoxime (IV) in 80 cc. abs.
EtOH yielded 0.35 g. 5,6-H2N(HO) deriv. of II, yellowish green scales, m. 220-2° (decompn.), unstable, and without
purification it was acetylated to 3,5,6-Ac(AcHN)(AcO) deriv. (V) of II, pale yellow scales, m. 169-71°. Catalytic reduction
of IV in glacial AcOH instead of in EtOH followed by heating with Ac2O gave 5,6-(AcHN)(AcO) deriv. of II, m. 205-6°,
further acetylated by refluxing 1.5 hrs. with Ac2O to V (identified by mixed m.p.). It was thus further confirmed that both
H2NCONHNH2 and HONH2 reacted with CO in the 5-position of adrenochrome.
~0 Citings

200. Absorption of acetic acid and glycerol from the rat stomach
By Herting, David C.; Embree, Norris D.; Harris, Philip L.
From American Journal of Physiology (1956), 187, 224-6. Language: Unavailable, Database: CAPLUS,
DOI:10.1152/ajplegacy.1956.187.2.224
cf. C.A. 50, 5865e. The absorption of AcOH from the pylorus-ligated rat stomach in 6 hrs. showed a typical log dose
response, with 2.0 millimoles being absorbed at the highest level administered. Under the same conditions, the amt. of
glycerol absorbed reached and maintained a const. level of approx. 0.4 millimoles. The gastric contents of rats
consuming a diet contg. 30% of distd., satd., partially acetylated monoglycerides contained an av. of 5.6 mg. (0.09
millimole) of free AcOH per rat.
~3 Citings
201. Usnic acid. XIII. Orientation and synthesis of usnolic acid

By Dean, F. M.; Evans, C. A.; Francis, Thomas; Robertson, Alexander
DOI:10.1039/jr9570001577
cf. C.A. 51, 2717b. Di-O-methyl-pyrousnic acid (I) was acylated to give 5-O-methylusnetic acid (II), whose acetate (III)
furnished 7-acetyl-6-hydroxy-4-methoxy-3'-methoxycarbonyl-2',5-dimethyl-3-methylene-4'-oxocyclopent-2'-ene-1'-spiro-2-
coumarin (IV), identical with Me O-methylusnolate, thus proving that usnolic acid (V) had the same pattern of aromatic
substitution as had usnic acid (VI). Usnetic acid (VII) from the demethylation of 4-O-methylusnetic acid (VIII) was
converted to Me usnolate (IX), the hydrolysis of which gave V, identical with the isomerization product of VI. AcOH (20
ml.) contg. 5 g. C-methylphloroglucinol triacetate satd. 10 min. at -10° with BF3 and the solid decompd. in hot 50% alc.
gave 4 g. 2,4-diacetyl-6-methylphloroglucinol (X), m. 170° (from dil. alc.). Attempted dimethylation of 1 g. X in refluxing
Me2 CO with Me2SO4 and 2 g. K2CO3 during 4 hrs. gave 0.4 g. 2,4-diacetyl-6-methylphloroglucinol trimethyl ether (XI),
prisms, m. 66-7°. Acidification of the alk. soln. gave 0.2 g. 2,4-diacetyl-6-methylphloroglucinol 1-methyl ether, m. 97°.
Use of MeI gave a similar result. 2,4-Diacetyl-6-methylphloroglucinol 5-acetate 1,3-dimethyl ether (XIa) (1 g.) warmed
with N NaOH gave 0.6 g. 2,4-diacetyl-6-methylphloroglucinol 1,3-dimethyl ether (XII), m. 64°. Acetylation of XII
regenerated XIa, either as platelets, m. 80° or cubes, m. 92°. XII (1 g.) and 0.8 g. BrCH2CO2Et refluxed 2 hrs. in 25 ml.
Et2CO contg. 1 g. K2CO3 and the product chromatographed gave 50 mg. Et 2,4-diacetyl-3,5-dimethoxy-6-
methylphenoxyacetate, m. 139-40° (from ligroine). Use of Me2CO, EtCOMe, or C6H6 as solvent gave no reaction. XII (1
g.) refluxed 8 hrs. with 1 g. allyl bromide and 2 g. K2CO3 in 15 ml. Me2CO gave 0.8 g. 2,4-diacetyl-6-methylphloroglucinol
5-allyl 1,3-dimethyl ether (XIII), b0.05 170°. XIII (1 g.) in MeOH contg. 1 g. 1% Pd-C shaken with H gave 0.4 g. XII and 0.5
g. 2,4-diacetyl-6-methylphloroglucinol 1,3-dimethyl 5-propyl ether (XIV), b0.05120°, identical with a specimen prepd. from
PrI and XII in the K2CO3-Me2CO method. XII (1 g.), 1.5 g. BrCH2CH:CHCO2Et, and 2 g. K2CO3 refluxed 6 hrs. in Me2
CO gave 1.3 g. Et γ-(2,4-diacetyl-3,5-dimethoxy-6-methylphenoxy)crotonate, m. 94°, which resinified in hot alc. NaOEt or
dil. NaOH. 3-Chloro-5,7-dihydroxy-4,8-dimethylcoumarilic acid (10 g.) and 15.5 g. PhCH2Br refluxed 4 hrs. in Me2CO
with 20 g. K2CO3 gave 15 g. 5,7-dibenzoyloxy-3-chloro-4,8-dimethylcoumarin (XV), m. 223° (from C6H6). XV (2 g.)
refluxed 10 min. with 0.6 g. KOH in 50 ml. Carbitol gave 1.5 g. 4,6-dibenzoyloxy-3,7-dimethylcoumarilic acid (XVI), m.
210° (decompn.); Me ester, m. 116-18° XVI stable in refluxing Carbitol, glycerol, or quinoline with or without Cu compds.
The acid chloride formed by PCl5 or SOCl2 was a greenish solid which with CH2N2 in Et2O 24 hrs. at -2° gave the crude
diazo ketone. No identifiable products were isolated when this ketone was treated with Ag2O or AgOBz in MeOH or
heated in PhCH2OH and PhNMe2. CO2 rapidly evolved for 10 min. from a mixt. of 5 g. 4,6-dimethoxy-3,5-
dimethylcoumarilic acid and CuCO3 at 220° and distn. gave 3 g. 4,6-dimethoxy-3,5-dimethylcoumarone, b0.05 125°, as a
yellow oil. 4,6-Dimethoxy-3,5-dimethylcoumaron-2-ylpyruvic acid (1.5 g.) in 15 ml. 2N NaOH at -5° oxidized 5 min. with 1
ml. 100 vol. H2O2 followed by chromatography on Al2O3 gave 0.9 g. I, m. 127° (from C6H6 and then dil. MeOH). I (0.8 g.)
and 0.6 g. Ac2O in 2 ml. Ac2O satd. with BF3 and left overnight gave 0.8 g. VIII, m. 166° (from C6H6); acetate (XVII), m.
134° (from C6H6). VIII (0.4 g.) and 1.5 g. MgI kept 1 hr. at 190° in N and the product refluxed with 2N H2SO4 gave a solid
which furnished 0.1 g. VII, m. 198-9°; diacetate, m. 173° (from aq. MeOH). 4,6-Dimethoxy-3,7-dimethyl-coumarilic acid
(5 g.) gave on decarboxylation 3 g. 4,6-dimethoxy-3,7-dimethylcoumarone (XVIII), b0.05 140°, m. 95-6°. XVIII (3 g.) in 75
ml. Et2O contg. 0.2 g. ZnCl2 and 3 ml. HCN satd. at 0° with HCl and after 3 days the aldimine HCl salt hydrolyzed with
refluxing H2O 10 min. gave 3 g. 2-formyl-4,6-dimethoxy-3,7-dimethylcoumarone (XIX), m. 158° (from dil. MeOH and then
C6H6); rhodanine deriv., red needles, m. 298° (from Me2CO). XIX (3 g.), 5 g. hippuric acid, 4 g. NaOAc, and 20 ml. Ac2O
kept 1.5 hrs. on the steam bath, then macerated with 100 ml. 50% alc., and left overnight gave the azlactone (XX),
orange needles, m. 238° (from Me2CO). XX (4 g.) and 8 g. KOH in 40 ml. 50% alc. refluxed 10 hrs., then cooled, dild.
with equal vol. H2O, satd. with SO2, after 3 hrs. the ppt. removed, and the clear soln. warmed 20 min. with 15 ml. HCl
gave 1.7 g. solid, m. 196°, which in 2N NaOH at -5° treated with H2O2 gave 1 g. 4,6-dimethoxy-3,7-dimethyl-2-
coumaronyl-acetic acid (XXI), m. 158-9° (from C6H6), purple color in warm H2SO4. Mg (0.12 g.), 0.18 g. MeOH, 0.6 g.
AcCH2CO2Me, and a drop CCl4 refluxed until no further change occurred, dild. with 10 ml. Et2O, refluxed 2 hrs. more,
then left overnight with the acid chloride from 1 g. I and 1 g. PCl5, and the mixt. refluxed 1 hr. and treated with a slight
excess 2N AcOH gave a crude dioxo ester, which on treatment 2 days at 0° with 2.5 ml. H2SO4 gave 0.6 g. 4,6-di-
methoxy-3'-methoxycarbonyl-2',5-dimethyl-3-methylene-4'-oxocyclopent-2'-ene-1'-spiro-2-coumaran (XXII), m. 141°, λ
235, 267, and 323 mµ (ε 28,200, 14,800, 11,300). XXI (1 g.) similarly treated gave 0.8 g. 4,6-dimethoxy-3'-
methoxycarbonyl-2',7-dimethyl-3-methylene-4'-oxocyclopent- 2'-ene-1'-spiro-2-coumarin. Only gums resulted when XXII
was treated with Ac2O and BF3. Thus attention was directed to introduction of this acetyl group at an earlier stage in the
synthesis. XVII (1 g.) in 15 ml. CHCl3 converted to the acid chloride at room temp. 15 min., then under reflux 0.5 hr., the
acid chloride refluxed 1 hr. with the methoxymagnesio deriv. of AcCH2CO2Me, unchanged XVII removed, and the
viscous orange oil treated 2 days at -2° with H2SO4 gave 0.25 g. Me O-methylusnolate, yellow prisms, m. 131°. XVII (0.5
g.) converted to the acid chloride, refluxed 1 hr. with the methoxymagnesio deriv. of AcCH2CO2Me, and the resulting
dioxo ester left 2 days at -2° with H2SO4 gave 100 mg. IX, yellow needles, m. 202° (from C6H6). The following hydrolysis
proved the most satisfactory. IX (0.05 g.) kept 15 min. at 60° in 2.5 ml. H2SO4.2H2O gave 0.03 g. V, yellow plates, m.
230° (from aq. MeOH).
~0 Citings
202. Transesterification of linseed oil with dihydric alcohols

By Mlejnek, Otakar; Artbauer, Jan; Chaternuch, L'udovit; Zvach, Jan
From Chemicky Prumysl (1957), 7, 41-4. Language: Unavailable, Database: CAPLUS
A mixt. of 1:2.35 ethylene glycol and diethylene glycol with alkali-refined linseed oil was used for the transesterification.
The products of this reaction probably included tri-, di-, and monoglycerides, diester of glycol and diglycol, monoester of
glycol and diglycol, glycerol, ethylene glycol and diglycol, and other compds. A complete analysis of the end products
was impossible. The final products were analyzed for alcs. and monoglycerides by sepn. with CCl4 and washing with
H2O. The CCl4 layer contained monoglycerides, and the water free alcs., glycerol, ethylene glycol, and diglycol.
Glycerol and ethylene glycol were detd. in the water layer by means of periodic acid according to Troy and Alsop (C.A.
43, 880a), ethylene diglycol by oxidation with K2Cr2O7, and the HO groups by acetylation, and reaction water with Karl
Fischer reagent (Mlejnek, C.A. 49, 13834d). The transesterification was followed on small samples by measuring the
dielectric const., refractive index, and soly. of the product dissolved in butanol by titrating with 75% EtOH. The
transesterification was done in one expt. at 190° without a catalyst with the following findings: free ethylene glycol and
HO groups reach a max. after 4 hrs. while free diethylene glycol and glycerol did not reach max. yet, while monoglyceride
reached equil. after 2 hrs. In a 2nd series of exps. at 180°, 190°, and 200° equil. was reached at 180° in 7 hrs., 190° in 5
hrs., and 200° in 4 hrs. Using 0.04% Pb catalyst at 190° the equil. is reached in less than 2 hrs.
~0 Citings
203. The constitution of a wheat starch dextrin

By Christensen, G. M.; Smith, F.
DOI:10.1021/ja01573a064
Com. wheat starch was heated 3 hrs. at 120° and then 5 hrs. at 140° in the presence of 2N HCl added previously as a
spray with mixing; the amt. 2N HCl used/g. starch corresponded to that required to give a pH of 3 when added to a mixt.
of 1 part starch and 2 parts H2O; the resulting dextrin (I) (canary type) was slightly yellow and sol. to 95% in H2O. I (50
g.) in 200 cc. H2O was fractionally pptd. with EtOH to give a no. of fractions; each fraction was dissolved in H2O and
repptd. with EtOH, centrifuged, washed with EtOH, Et2O, and petr. ether, and dried in vacuo at 50°. In this manner were
obtained the following fractions (wt. in g., total cc. EtOH added, color of ppt. with iodine, and [α]25 D of a 1% soln. in H2O
given): (1) 1.5, 7, purple, 175°; (2) 2.4, 17, purple, 153°; (3) 2.2, 37, purple, 153°; (4) 2.6, 52, purple-lavender, 154°; (5)
0.6, 72, purple-lavender, 155°; (6) 1.0, 92, purple-lavender, 158°; (7) 0.4, 112, purple-lavender, 162°; (8) 1.7, 137,
lavender, 160°; (9) 7.1, 157, lavender, 156°; (10) 18.5, 207, lavender, 130°; (11) 2.1, 257°, lavender-red-brown, 122°;
(12) 5.8, 307, red-brown, 121°. Fraction 10 (17.6 g.) in 100 cc. HCONMe2 added slowly with stirring to 100 cc. pyridine
and 100 cc. Ac2O with cooling, kept 10 hrs. at room temp., poured with stirring into 8-10 vol. ice H2O, and filtered, and
the white amorphous residue washed with abs. EtOH, Et2O, and petr. ether, and dried in vacuo yielded 24 g. acetylated
dextrin, [α]25 D 158° (c 0.6, CHCl3), which reacetylated 3 hrs. with 5 parts 1:1 Ac2O-pyridine yielded 23.5 g. I acetate (II),
[α]25 D 155° (c 0.6, CHCl3), contg. 44.7% Ac. II (18.5 g.) repptd. from CHCl3 with increasing amts. of petr. ether gave the
following fractions (wt. in g., total cc. petr. ether added, and [α]25 D of a 1% soln. in CHCl3 given): (1) 12.7, 55, 156-8°; (2)
2.4, 75, 151°; (3) 2.3, 115, 166°; (4) 0.4, 145°, -. II (fraction 1) (3 g.) in 10 cc. 10% aq. KOH and 15 cc. Me2CO stirred 1
hr. at room temp. and 0.5 hr. at 50°, the soln. cooled, neutralized with AcOH, and poured into EtOH, and the ppt.
centrifuged, dissolved in H2O, repptd. with EtOH, and dried in vacuo at 50° gave I, powder, [α]24 D 132° (c 0.6, H2O). I
(0.9 g.) treated at 5° in the dark with 100 cc. 0.1N NaIO4 gave the following results (reaction time in hrs., [α]25 D, moles
anhydrohexose/mole HCO2H produced, and moles NaIO4 consumed/mole anhydrohexose unit given): 0.08, 77°, 25.9,
0.66; 52, 19°, 12.7, 1.01; 138, 19°, 9.0, 1.06; 213, 18°, 7.9, 1.06. The remaining oxidation mixt. treated with aq. BaCl2,
and centrifuged, the supernatant soln. treated at room temp. with 4 times the theoretical amt. of NaBH4, agitated
periodically during 3 hrs. and filtered, the residue washed with cold EtOH, redissolved in H2O, repptd. with EtOH,
acidified with AcOH, and evapd. to dryness, the residue shaken 5 min. with 30 cc. 1% HCl-MeOH and evapd. in vacuo at
40°, the HCl treatment repeated, and residue stirred 2 hrs. at room temp. with 0.5N HCl, warmed 1 hr. at 50°, neutralized
with BaCO3, passed through Amberlite IR-120 and then Duolite A4, and evapd. gave a sirup, [α]25 D 8.5° (c 2.7, H2O),
which chromatographed on Whatman No. 1 paper with PrOH-H2O azeotrope showed the presence of glucose, erythritol,
and glycerol in the molar ratio 1.0:7.5:1.0. II (8.5 g.) in 190 cc. Me2CO treated with 90 cc. Me2SO4 and 250 cc. 30%
Me2SO4, and heated 0.5 hr. on the water bath, the ppt. washed by decantation with boiling H2O, dissolved in Me2CO,
and subjected to 3 treatments with 6 g. Ag2O and 30 cc. MeI, the excess MeI evapd., the residue extd. with Me2CO, and
the ext. centrifuged and evapd. gave 4.20 g. brown sirup; 4.10 g. in 40 cc. Me2CO fractionally pptd. with petr. ether gave
an essentially homogeneous methylated dextrin (III), [α] 182° (c 1, CHCl3), contg. 43.5% MeO. The mother liquor from
the product of the 1st methylation was extd. with CHCl3 and the recovered II was further methylated in the usual manner.
III (3.30 g.) refluxed 10 hrs. with 3.5% HCl-MeOH, neutralized with Ag2CO3, filtered, and evapd. in an air stream, the
resulting Me glycosides (3.42 g.) heated 19 hrs. at 98° with 40 cc. N H2SO4, the soln. neutralized with BaCO3 and
filtered, the residue washed with H2O, the combined aq. filtrates extd. with CHCl3, and the sirup (1.75 g.) from the CHCl3
ext. and that (1.43 g.) from the aq. layer subjected to a partition chromatography on cellulose-hydrocellulose with
EtCOMe-H2O azeotrope gave the following compds. (Rf and wt. in g. given): 2,3,4,6-tetramethyl-D-glucose (IV), 0.82,
0.373; 2,3,6-trimethyl-D-glucose (V), 0.51, 2.290; 2,3-dimethyl-D-glucose (VI), 0.18, 0.119; 2,6-isomer (VII) of VI, 0.15,
0.240; 2-methyl-D-glucose (VIII), 0.042, 0.029; 3-isomer (IX) of VIII, 0.062, 0.010. IV [20.7 mg., m. 89° (from Et2O), [α]24
D 81.5° (c 5, H2O; equil.)] in 2 cc. dry pyridine and 48.3 mg. p-O2NC6H4COCl heated 40 min. at 80-5°, cooled, treated
with a few drops of H2O, poured into 10 cc. cold satd. aq. NaHCO3 and extd. with CHCl3, and the residue from the ext.
crystd. from aq. MeOH gave the mono-p-nitrobenzoate, m. 101-2°. V (2.29 g.), m. 112-15° (Et2O), [α]24 D 62° (c 1, H2O;
equil.), gave similarly the 1,4-di(p-nitrobenzoate), m. 190-1°, [α]24 D -32° (c 2, CHCl3). VI, m. 85-6°, [α]24 D 49° (c 4,
MeOH), with PhNH2 yielded N-phenyl-D-glupyranosylamine 2,3-di-Me ether, m. 134° (EtOAc), [α]22 D -83° (c 4, CHCl3).
VII, sirup, [α]24 D 63° (c 5, H2O; equil.), treated with p-PhN:NC6H4COCl in pyridine gave the 1,3,4-tris(p-
phenylazobenzoate), m. 202-6° (from EtOAc-petr. ether), [α]23 D -260° (c 0.1, CHCl3). VIII, m. 157-8° (from EtOH),
showed [α]24 D 65° (c 1, H2O; equil.). IX, m. 157-8°, showed [α]24 D 56° (c 1, H2O; equil.). The hydrolyzate of III yielded
in addn. 10 mg. material showing the Rf value 0.062 of D-glucose but only a rotation of [α]24 D 17° (c 0.2, H2O), indicating
that only 1/3 of the material could have been glucose.
~2 Citings
204. The acetylation process in psoriasis

By Caccio, I.; Pochy-Riano, R.
From Ann. ital. dermatol. e sifilog. (1957), 12, 3-15. Language: Unavailable, Database: CAPLUS
The acetylation index (I) (per cent of (1 g.) injected p-aminobenzoic acid, as found in acetylated form in blood or urine 1
and 3 hrs., resp., after the injection) averaged 51.94 and 39.85 in the urine, and 48.13 and 35.33 in the blood of 10
healthy and 18 diseased individuals, resp. In 5 patients, I in urine averaged 39.02 and 43.60, resp., 7 days before and 30
min. after an injection of 0.5 g. fructose-1,6-phosphate intravenously and 10 mg. adenosinetriphosphate in glycerol soln.
with addn. of phosphate metabolites, intramuscularly. This supports the view of the importance of phosphoric bonds with
high energy potential in the activation of enzymic processes connected with the activity of coenzyme A, and the imperfect
peripheral utilization of carbohydrates in psoriasis.
~0 Citings
205. Synthesis of indenoquinolines

By Campbell, Neil; Temple, Arthur F.
DOI:10.1039/jr9570000207
To 12.5 g. vigorously boiling 2-nitrofluorene (I) in 180 ml. EtOH was added 10 g. finely divided Fe powder, 250 ml. concd.
HCl added dropwise during 1.5 hrs., and the whole refluxed 2 hrs. and cooled gave 89-96% 2-aminofluorene-HCl (II), m.
125-6° (from EtOH). I (5 g.) in 200 ml. AcOEt and Raney Ni at 60 lb./sq. in. and room temp. gave 82% 2,2'-
azoxyfluorene. NaN3 (1 g.), 2.2 g. 2-acetylphenanthrene, and 15 g. Cl3CCO2H heated 4 hrs. at 60° (bath temp.), 0.2 g.
NaN3 added, the heating continued 3 hrs. and the whole poured on ice gave 72% 2-acetamidophenanthrene (III), m.
225-6° (from EtOH); III, 100 ml. MeOH, and 15 ml. concd. HCl, followed by NaOH, gave 92% 2-aminophenanthrene (IV),
m. 85°. IV (5 g.), 11 g. glycerol (VI), 7 ml. concd. H2SO4, and 9 g. As2O5 refluxed 4 hrs., the whole poured on ice, the
ppt. refluxed with HCl, and the whole treated with NaOH gave 69% 3-azachrysene (C.A., 1-azachrysene) (VII), m. 129-
30° (from PhMe). To 0.1 g. VII in 5 ml. AcOH was added 0.1 g. Cr2O3 in 1 ml. H2O, the whole refluxed 2-3 min., concd.
in vacuo, the residue washed with H2O, and the H2O-insol. part sublimed at 190°/0.1 mm. or recrystd. from xylene-petr.
ether gave 10% 3-azachrysene-7,8-quinone (VIII), crimson needles, m. 285-6°. VIII (0.02 g.) and 6 ml. 5% KOH heated
36 hrs. on the steam bath while blown with air and the whole evapd. to 0.5 vol. gave 50% 1'-oxoindeno[2',3',5,6]quinoline
(IX), yellow needles, m. 178-9° (from (EtOH). 1'-Oxoindeno[3',2',6,7]quinoline (X) (1 g.) added in portions to 3 g. KOH
and Ph2O at 180°, the whole kept 2 hrs. at 180°, poured into C6H6, the K salt sepd., added to 3 ml. concd. H2SO4, and
the whole heated 1 hr. at 100°, poured into water, and treated with NaOH gave IX. IX (0.2 g.), 10 ml. HO(CH2)3OH, 0.5
ml. 90% N2H4.H2O, and 0.1 g. NaOH heated to 205° (without condenser), then refluxed 2 hrs., the whole concd. in
vacuo, the residue poured into H2O, extd. with Et2O, the Et2O exts. dried and concd. gave an oil, which gave a picrate
(XI). The XI was partitioned between C6H6 and aq. NaOH, the C6H6 soln. chromatographed and the chromatogram
eluted with C6H6 to give indeno[2',3',5,6]quinoline (XIA), m. 150° (from C6H6-petr. ether). 2-Amino-3-nitrofluorene (2 g.),
9 g. VI, 4.6 g. As2O5, and 2 g. concd. H2SO4 heated 3 hrs. (no temp. specified), the whole poured into H2O, the tarry
product sepd., dried, dissolved in C6H6, and the C6H6 soln. chromatographed and eluted with C6H6 gave 2% X. 4-
Aminofluoranthene (3 g.), 12.6 g. VI, 4.0 g. concd. H2SO4, and 6.4 g. As2O5 heated 6 hrs., the whole poured into H2O,
treated with excess NaOH, extd. with Et2O, the Et2O concd. and the residue in C6H6 chromatographed gave 12%
pyrido[3',2',3,4)fluoranthene, pale yellow needles, m. 169-70° (from EtOH). 2-Methylindeno[3',2',6,7]quinoline-4-
carboxylic acid (XII) (Neish, C.A. 43, 193a) gave a Me ester, needles, m. 168-70°; XII decarboxylated by heating with
CaO gave a red-oil distillate, which after chromatography in C6H6 gave 2-methylindeno[3',2',6,7]quinoline (XIII), needles,
169-70° (from C6H6-petr. ether). XIII (0.5 g.), 0.5 g. SeO2, 70 ml. dioxane, and 5 ml. H2O refluxed 3 hrs., 0.2 g. C added,
the whole filtered, the filtrate evapd. to 0.5 vol. and then dild. with H2O gave a permanent ppt.; the ppt. was dissolved in
boiling EtOH (Hg added to sep. Se), the whole refluxed 1 hr., C added, the whole filtered, and the filtrate evapd. to 0.5
vol. gave 40% aldehyde (XIV), needles, m. 221-2°. XIV (0.3 g.), 200 ml. pure Me2CO and 2 ml. 30% H2O2 refluxed 3
hrs. and distd. gave 57% indeno [3',2',6,7]quinoline-2-carboxylic acid (XV), yellow crystals, m. 238-9° (from AcOH); XV
and CaO gave indeno[3',2',6,7]quinoline (XVI), m. 132-3°. 2-Aminofluoren-9-ol(3 g.), EtOH, and 3 ml. AcCO2H refluxed 5
hrs. gave 40% crude quinaldinic acid deriv. (XVII), m. 300-10° (from PhNO2); Me ester, m. 227-8°. XVII (1 g.), 10 ml.
quinoline, and 0.1 g. Cu refluxed 2 hrs., the whole steam distd., and a C6H6 soln. of the residue chromatographed and
eluted with C6H6 gave 0.35 g. 2-methyl-l'-oxoindeno[3',2',6,7]quinoline, yellow needles, m. 203-4° (from C6H6-petr.
ether); 2,4-dinitrophenylhydrazone, crimson crystals, high unspecified m.p. XVII and CaO gave presumably XIII. XVII,
HO(CH2)3OH, and N2H4.H2O as above also gave XIII. 2-Aminofluorene (XVIII) (2.1 g.), 4 ml. concd. HCl, 3 g.
paraldehyde, and 1.5 g. ZnCl2 warmed 1.5 hrs. on the steam bath, the whole poured into H2O containing 5 g. NaOH,
extd. with C6H6, the C6H6 exts. washed with H2O, concd. to a small vol. and chromatographed gave XIII. 2,4-
Dimethylindeno [3',2',6,7)quinoline could not be prepd. by the procedure of Buu-Hoï and Royer (C.A. 41, 2713a) since
sulfonation occurred; the following procedure is recommended for small scale work. The anil from XVIII and Ac2CH2 (1
g.), 10 ml. glacial H3PO4, and 10 g. P2O5 heated on the water bath until a deep yellow color formed, the whole poured
into an excess of aq. NaOH, extd. with Et2O, and the Et2O exts. concd. gave 79% 2,4-dimethyl[3',2',6,7]quinoline (XIX),
prisms, m. 158° (from C6H6-petr. ether). Me 2-methylindeno[3',2',6,7]quinoline-4-carboxylate (0.5 g.) in 100 ml. dry C6H6
added to 0.5 g. LiAlH4 in 200 ml. dry Et2O, the whole refluxed 2 hrs., the solvents distd., 100 ml. 1% aq. NaOH added
cautiously, and any residual solvent distd. gave 71% crude 4-hydroxymethyl-2-methylindeno[3',2',6,7]quinoline (XX), m.
225-7°. The dried XX (1 g.) and 6 g. Zn dust distd., and the red oil in C6H6 chromatographed and eluted with C6H6 gave
20% pure XIX, m. 158° (from C6H6-petr. ether). To 1.1 g. AcCO2H and 2.0 g. BzH in 25 ml. boiling EtOH was added
gradually 3 g. XVIII in 10 ml. boiling EtOH to give 65% 2-phenylindenocinchoninic acid (XXa), m. 265-70°;
decarboxylation of XX in quinoline with Cu or, preferably, distn. with CaO, gave 40% 2-phenyl-indenoquinoline (XXb), m.
222-3°. 2-Bromo- and 2,7-dibromofluorene were unaffected by a 4-hr. reflux with HI (d. 1.94) and red P; however, under
these conditions, 2,3,7-tribromofluorene gave 85% 2,7-dibromofluorene and 2-amino-3,7-dibromofluorene (XXI) gave 2-
amino-7-bromofluorene (85% yield, isolated as the Ac deriv.). Fluorene and Br in CHCl3 at 0° gave 2-bromofluorene
(XXII) contaminated with 2,7-dibromofluorene; the crude XXII (60 g.) in 500 cc. AcOH at 50° treated with 500 cc. concd.
HNO3, the temp. gradually raised to 80°, kept 5 min. at 80°, the whole cooled, the solid filtered off, and washed with a
little AcOH and much H2O gave 67% 2-bromo-7-nitrofluorene, m. 236° (from AcOH); reduction with Fe powder and HCl
as above gave 90% 7-amino-2-bromofluorene (XXIII), m. 140-1° (from aq. EtOH). Acetylated XXIII (10 g.) in 45 cc.
PhNO2 and 7 g. Br kept 3 hrs. at room temp. and the whole steam distd. left 80% 2-acetamido-3,7-dibromofluorene
(XXIV), m. 272° (from AcOH). XXIV (10 g.) and 100 cc. 70% H2SO4 refluxed 1.5 hrs., the whole poured on ice, and the
mixt. treated with excess NH3 gave 80% XXI, microcrystals, m. 133-4° (from AcOH). The following ultraviolet data are
also given for several compds. (all in 95% EtOH) (log E in parentheses): X, λmax. 281, 378 mµ (4.81, 2.49), λmin. 228, 368
mµ (4.18, 2.48); XIA, λmax. 266, 325, 340, 350, 425 mµ (4.72, 3.31, 3.51, 3.56, 2.84), λmin. 237, 314, 327, 350, 380 mµ
(3.97, 3.17, 3.30, 3.42, 2.77); XXb, λmax. 228, 242, 248, 254, 272, 316, 3.24, 3.39, 358, 370 mµ (4.02, 3.74, 3.79, 3.89,
4.10, 3.53, 3.59, 3.63, 3.74, 3.83), λmin. 227, 240, 245, 250, 256, 301, 318, 331, 348, 362 mµ (3.84, 3.69, 3.69, 3.73,
3.86, 3.44, 3.52, 3.56, 3.63, 3.65.)
~3 Citings

206. Physical properties and chemical composition of the flavoring substances used in the manufacture of
confections. I
By Gyorbiro, Karoly
From Elelmezesi Ipar (1957), 11, 171-5. Language: Unavailable, Database: CAPLUS
Methods for the evaluation of natural and synthetic vanilla and menthol flavoring substances were developed. Vanilla
ext. (I) is a mixt. of burbonal, glycerol, and EtOH. The EtOH content is detd. by distn. and the sp. gr. by means of a
pycnometer. The burbonal and glycerol content can be calcd. from these data by using the formula glycerol % = (100da)
- (e% × de)/dgl, where da is the sp. gr. of I, de is the sp. gr. of EtOH, dgl is the sp. gr. of glycerol, and e% is the
percentage of EtOH in I. After the EtOH is distd. off, the burbonal and glycerol can be sepd. by dissolving the former in
ether or CHCl3. Burbonal can be identified by the formation of a blue coloration if heated with an aq. FeCl3 soln. and can
be quant. detd. by titrn. with a 0.01N NaOH soln. by using phenolphthalein as indicator. Menthol ext. (II) can be
evaluated by its optical rotation, n, vacuum drying residue content, extn., and menthol content. Vacuum drying is carried
out at 40° under 100-mm. Hg pressure for 16 h. Extn. is conducted by adding 2 g. NaCl and 20 mL. CHCl3 to 20 g. II in a
separatory funnel and draining the CHCl3 portion. The residue is shaken with 15 mL. CHCl3, and the liq. phase is added
to the aq. phase in the funnel. After sepn. the CHCl3 phase is added to the previous CHCl3 phase and the two are dried
with calcinated Na2SO4 followed by evapn. The oily residue is weighed. Menthol content is detd. from the oily residue
by acetylating a 10-g. sample with 10 mL. Ac2O and 2 g. H2O-free AcONa for 1 h. at low heat. Approx. 2 g. acetylated
substance is then neutralized with a 0.1N KOH soln. in PrOH (phenolphthalein indicator). Ten ml. of the above KOH
soln. is added and the excess titrated with a 0.5N HCl soln. To det. the menthol content of II from the acetylated
substance it is necessary to establish the initial menthyl acetate content (if any) by the same procedure. The results can
be calcd. from the following formulas: [(sv - so) × 0.0182 × Mm × 100]/(Ms × BII) = Mme and [(sv - sac) × 0.0183 × Mm ×
100]/(Ms × BIIa) = Mt, where sv is the no. of ml. KOH for the blank test of the alkali, so is the no. of mols. HCl used in
titrating the excess alkali in the original oil, Mm is the mol. wt. of menthol (156.26), Mme is the menthol content (in %) of
the menthyl acetate in II, sac is the no. of ml. HCl used in titrating the excess alkali in the acetylated product, Ms is the
mol. wt. of HCl, BII is the wt. of the oily residue sample, BIIa is the wt. of the acetylated substance sample, and Mt is the
menthyl acetate content (expressed as menthol %) in the acetylated product.
~0 Citings
207. New method for the pre-coloration of serum lipoproteins

By DiLeo, F. P.; Betti, R.; Solinas, P.
From Minerva Medica (1957), 3714-16. Language: Unavailable, Database: CAPLUS
α-and β-Lipoproteins can be differentiated upon paper electrophoresis by various lipidesol. dyes. To obtain clearer
results, reduce the amt. of washing and lower the blank values, Sudan Black B (I), purified and acetylated according to
Lillie and Burtner (C.A. 48, 9424c) was added as a satd. alc. soln. to serum in the ratio 1:10. After 30 min. at room temp.
the dye was found in the lipide part of the lipoprotein. The alc. was removed by a current of air or N, excess dye pptd.
and removed by centrifugation. Electrophoresis of 5 microliters gave a perfect blank and a distinct sepn. after 4-5 hrs.
(McDonald and Bermes, C.A. 49, 12583c). A better solvent than alc. for this purpose is diacetin (II), which does not ppt.
protein nor alter the serum significantly, nor disturb the electrophoresis. To 1 ml. of serum was added slowly with stirring
0.1 ml. of satd. soln. of I in II. Pptd. I was removed by centrifugation and electrophoresis was done in 5-6 hrs. with α-
and β-fractions showing blue zones on perfectly white background. After drying at 80° they could be read directly, or
could be treated with glycerol or better silicone 200/100.
~0 Citings
208. Monoacetylated phosphatide acids

By Prigge, Richard; Helmert, Erica
From No Corporate Source data available (1957), DE 1007310 19570502, Language: Unavailable, Database:
CAPLUS
Glycerophosphoric acids were acylated with trisubstituted acetic acids or derivs. thereof and the resulting monoacylates
esterified with phosphoric acid or derivs. thereof to give the title compds., useful as tuberculostatics. Thus, a mixt. of
32.8 α-glyceryl ester of methylidi(p-tolyl)acetic acid (prepd. from equimolar amts. of Na methyldi(p-tolyl)acetate and α-
monochlorohydrin at 120°) and 14.5 g. P2O5 was heated 1 hr. at 125°, then heated 1 hr. with 10 vols. 50% EtOH, the
EtOH distd., the aq. layer decanted, the residual oil made alk. by addn. of N NaOH, extd. with Et2O, the aq. layer freed
from Et2O, and the residue acidified to give α-[methyldi(ptolyl)acetyl]-β-glycerophosphoric acid, viscous oil. Similarly
were prepd. the following substituted β-glycerophosphoric acids (substituent and m.p. given): α-[4-hydroxy-2,5-
dimethylphenyl)diphenylacetyl], oil; α-[α-(2,5-dimethylphenyl)acryloyl], oil.
~0 Citings
209. Fluorescent derivatives of 1,2,3-triazole. Introductory remarks. II. Sulfonated benzo- and naphthotriazoles
derived from 4,4'-diaminosfilbene-2,2'-disulfonic acid
By Dobas, Jaroslav; Pirkl, Jaromir; Hanousek, Vitezslav
From Chemicke Listy pro Vedu a Prumysl (1957), 51, 1113-21. Language: Unavailable, Database: CAPLUS
Further expts. revealed that the triazole ring is a chromophore, the effect of which can be compared with that of the
groups CO and CH:N. Expts. with model compds. showed that the triazole ring substituted in position 2 is the bearer of
visible fluorescence, whereas the 1-substituted ring does not show fluorescence in the visible region. Tetrazotizing 0.025
mole 4,4'-diaminostilbene-2,2'-disulfonic acid (I) in the usual way, dropping the resulting suspension in the course of 30
min. at 5-10° to a soln. of 0.0525 mole Na 2-naphthylamine-5-sulfonate and 0.15 mole AcONa in 500 ml. H2O, stirring the
mixt. 2 hrs. at 5-10° heating to 80°, adding portionwise 0.075 mole Na2CO3, stirring another hr., dilg. to 2 l., adding at 35°
75 ml. 25% NH4OH, heating to 50°, adding soln. of 0.1 mole CuSO4 in 200 ml. H2O and stirring 30 min. at 90-5°,
acidifying the decolorized mixt. with 70 ml. concd. HCl at 60°, salting out the dye with 10% solid NaCl (by vol.) and
washing the product with 20% NaCl soln. gave 85-90% Na 4,4'-bis(2-naphtho[l,2]triazolyl)stilbene-2,2',6'',6'''-
tetrasulfonate (II), RS 0.03. When the oxidation was carried out with NaClO instead of CuSO4, side reactions took place
characterized by cleavage of the mol. at the site of the central C-C double bond, yielding 2-(4'-
formylphenyl)naphtho[1,2]triazole-3',6-disulfonic acid (III) and 2-(4'-carboxyphenyl)naphtho[1,2]triazole-3',6-disulfonic
acid (IV). III and IV were also obtained by oxidizing II with the equiv. amt. of aq. KMnO4 at 80°. In analogy with the
prepn. of II were obtained Na 4,4'-bis(2-naphtho[1,2]triazolyl)stilbene-2,2',5'',5'''-tetrasulfonate (V) (RS 0.03) and Na 4,4'-
bis(2-naphtho[1,2]triazolyl)stilbene-2,2',7'',7'''-tetrasulfonate (VI), RS 0.03. Na 4-(p-aminobenzoylamino)-4'-(2-
naphtho[1,2]triazolyl)stilbene-2,2',5''-trisulfonate (VII) (RS 0.03), obtained by treating the starting 4-amino compd. [cf.
BIOS Misc. Rept. 20, Appendix 15(1945)] with p-O2NC6H4COCl in aq. soln. at 80° in the presence of AcONa and
reducing the product with Fe according to Béchamp, was purified by repeated pptn. from aq. alc. By analogical
procedure was obtained di-Na H 4-amino-4'-(2-naphtho[1,2]triazolyl)stilbene-2,2',6''-trisulfonate (VIII) (RS 0.26), purified
by prepg. its Ac deriv., recrystg. it from H2O, and sapong. by boiling with 5% NaOH. Similarly was prepd. Na 4-
acetamido-4'-(2-naphtho[1,2]triazolyl)stilbene-2,2',6''-trisulfonate, RS 0.16. Treating VIII with BzCl at 40-50° in 20%
pyridine gave Na 4-benzamido-4'-(2-naphtho[1,2]triazolyl)stilbene-2,2',6''-trisulfonate (RS 0.03); treating VIII with p-
O2NC6H4COCl in analogy with the prepn. of VII gave Na 4-(p-aminobenzamido)-4'-(2-naphtho[1,2]triazolyl)stilbene-
2,2',6''-trisulfonate, RS 0.03. When PhNCO (6 g.) was added at 10-20° under vigorous stirring and cooling to a soln. of
0.04 mole VIII in 400 ml. H2O, the mixt. stirred 12 hrs., dild. to 450 ml., heated to 85° and filtered, Na 4-phenylureido 4'-
(2-naphtho[1,2]triazolyl)stilbene-2,2',6''-trisulfonate (RS 0.03) was obtained, on cooling and recrystg. from H2O. Dropping
suspension of 0.1 mole diazotized I in 800 ml. H2O in the course of 30 min. to a soln. of 0.22 mole m-(H2N)2C6H4 in 1.7 l.
H2O and 0.15 mole Na2CO3, dilg. the mixt. with 500 ml. H2O, stirring 10 hrs., heating to 85°, salting out the dye with 10%
solid NaCl, sepg. at 60° and washing with 10% NaCl soln., dissolving the dye in 2.5 l. H2O, adding 400 ml. 20% NH4OH
and soln. of 0.8 mole CuSO4 in 600 ml. H2O, heating the mixt. 30 min. to 95°, adding 200 g. glycerol and 200 ml. 20%
NH4OH and heating to 98° for about 2 hrs., acidifying the soln. with 65 ml. concd. HCl at 90° sepg. the product at 85°
washing with hot H2O and drying gave 28 g. 4,4'-bis(5-amino-2-benzotriazolyl)stilbene-2,2'-disulfonic acid (RS 0.03).
Pouring 0.05 mole I at room temp. to a suspension prepd. by acidifying a soln. of 0.11 mole Na 2,6-toluylenediamino-4-
sulfonate in 250 ml. H2O with 100 ml. 2.5N HCl, stirring 1 hr., adding dropwise in the course of 5 hrs. under stirring 100
ml. 2.5N Na2CO3, stirring 10 hrs., adding a soln. of Na2CO3, dissolving the sepd. cake in 300 ml. H2O and 50 ml. NH4OH
at 80°, adding soln. of 0.4 mole CuSO4 in 200 ml. H2O, 200 ml. 20% NH4OH, and 100 ml. pyridine, heating the resulting
suspension 5 hrs. under stirring to 90-5° cooling, sepg. the product, dissolving it in 1000 ml. H2O and 100 ml. pyridine,
heating the soln., adding a little Na2S2O4 and Na2CO3, removing the sepd. metallic Cu with C and cooling the filtrate
gave 33 g. cryst. Na 4,4'-bis(4''-methyl-5''-amino-2''-benzotriazolyl)stilbene-2,2',7'',7'''-tetrasulfonate (IX), RS 0.03. When
acetylated with excess Ac2O in aq. Na2CO3 medium at 40°, IX gave Na 4,4'-bis(4''-methyl-5''-acetamido-2''-
benzotriazolyl)stilbene-2,2',7'',7'''-tetrasulfonate, RS 0.1. Heating 0.05 mole Na salt of I in 300 ml. H2O under stirring 8
hrs. to 170°/8 atm. with 0.1 mole K salt of 2-nitrochlorobenzene-4-sulfonic acid and 0.2 mole MgO, dilg. to 1 l., adding 40
ml. 2.5N NaOH, filtering at 80°, salting out the filtrate with 15% solid NaCl, sepg. and reducing the product according to
Béchamp, salting out the resulting Na 4,4'-bis(2''-amino-4''-sulfophenylamino)stilbene-2,2'-disulfonate with 20% solid
NaCl and acidifying, purifying by repeated salting-out, dissolving in 800 ml. H2O, acidifying the soln. with 100 ml. 10N
HCl and adding dropwise at 10° 32 ml. 2.5N NaNO2 gave 24 g. Na 4,4'-bis(1-benzo-triazolyl)stilbene-2,2',5'',5'''-
tetrasulfonate (RS 1.0) which sepd. spontaneously. 1-Methylbenzotriazole, m. 65°, and oily 2-methylbenzotriazole, b15
102°, were prepd. according to Krollpfeiffer, et al. (C.A. 29, 21659). Adding 0.05 mole o-ONC6H4NHAc to a soln. of 0.05
mole p-H2NC6H4SO3H in 120 ml. EtOH and 40 ml. pyridine, adding 80 ml. AcOH, boiling 30 min., removing 200 ml. of
the mixt. by steam-distn., treating the residue with 150 ml. 40% NaOH and boiling 1 hr., cooling down, sepg. the dye,
dissolving it in 1 l. H2O, oxidizing at 80° with excess NaClO, cooling, sepg. the product and recrystg. 3 times from H2O
gave 1 g. Na 2-phenylbenzotriazole-4'-sulfonate. Heating 0.06 mole K 2-nitrochlorobenzene-4-sulfonate with 0.07 mole
PhNH2 and 0.15 mole MgO in 150 ml. H2O 8 hrs. under stirring to 170°/8 atm., dilg. to 200 ml. with H2O, filtering off
excess MgO while hot, and salting out the filtrate with 20% KCl gave cryst. K 2-nitrodiphenylamino-4-sulfonate which
was reduced with Fe according to Béchamp, Fe removed with Na2CO3, the filtrate acidified with HCl, a soln. of N Na-
NO2 added dropwise under stirring at 10° and the product salted out with 20% NaCl to give 6.5 g. Na 1-
phenylbenzotriazole-5-sulfonate. Adding to soln. of 0.2 mole Na sulfanilate in 300 ml. H2O 120 ml. 20% soln. of AcONa,
then under stirring at 70° in the course of 2 hrs. a soln. of 0.2 mole 2,4-dinitrochlorobenzene in 300 ml. EtOH divided in 3
portions, refluxing 8 hrs. and distg. 300 ml., cooling, purifying the crystd. product by dissolving in dild. HCl, filtering with
C, and salting out with NaCl gave 44 g. crude Na 2,4-dinitrodiphenylamino-4'-sulfonate which was suspended (0.075
mole) in 75 ml. EtOH; 0.125 mole Na2S and 0.130 mole NH4Cl in 15 ml. H2O were added, the spontaneously warmed
mixt. cooled to 50° and stirred at 50° 1 hr., cooled, the sepd. Na 2-amino-4-nitrodiphenylamino-4'-sulfonate purified by
filtering with C and salting out, converted to the triazole by HNO2 and reduced according to Béchamp gave 17 g. Na 1-
phenyl-5-aminobenzotriazole-4'-sulfonate. Characteristic properties of the prepd. dyes are given in table. Only II can be
used as a brightening agent, others being unsuitable. Dyes II, V, and VI have greater light-fastness than those described
in the preceding communication. Ultraviolet spectra of the prepd. compds. are charted.
~1 Citing

210. Epoxidized fatty acid diacetylated glycerides, for use as stabilizers and plasticizers in synthetic resins
By Ault, Waldo C.; Feuge, Reuben O.
From No Corporate Source data available (1957), GB 775326 19570522, Language: English, Database: CAPLUS
Unsatd. natural glycerides are converted to monoglycerides, acetylated, and then epoxidized to form products useful as
stabilizers and plasticizers in synthetic resins. Epoxidized oils have limited compatibility when used as stabilizers and
plasticizers in synthetic resins. Compatibility can be improved by epoxidizing, instead, diacetylated monoglycerides. The
products are of value as plasticizers-stabilizers for poly(vinyl chloride), copolymers of vinyl chloride and vinyl esters or
vinylidine chloride, cellulose esters, nitrocellulose, and chlorinated rubber. Preferably 20-40% by wt. of the plasticized
compn. is used. The triglyceride is first converted to the monoglyceride. This is acetylated and then epoxidized. Thus,
200 g. of cottonseed oil is converted to the monoglyceride by adding 31.4 g. of glycerol and 0.2 g. of NaOH, heating, and
agitating for 5 hrs. at 200° under an inert atm. The product (180 g.) is acetylated with Ac2O for 1 hr. at 110° under an
inert atm. The product is then stirred in hot water for 10 min., washed again with water, and dried by passing an inert gas
through in vacuo. The product (100 g., I no. 72.8) is treated with 190 ml. of a 20% soln. of peracetic acid in AcOH,
dropwise and with stirring, at 20-5°. The product is then stirred for 3 hrs. at 20-5°. The product is poured into a large vol.
of water, extd. with ether, washed with water, dried, and the ether is evapd. A table is given showing properties of a resin
prepd. with this type, as against one with dioctyl phthalate. Significant improvement is noted in light stability.
~1 Citing
211. Bacteria. IV. A C20-acid from violacein

By Ballantine, J. A.; Barrett, C. B.; Beer, R. J. S.; Boggiano, B. G.; Clarke, K.; Eardley, Stephen; Jennings, B. E.;
Robertson, Alexander
DOI:10.1039/jr9570002222
cf. C.A. 49, 10925i. Reductive hydrolytic fission of violacein (I) gave, in high yield, a colorless acid, C20H16O5N2, which
on the basis of chem. and spectroscopic evidence was formulated as a γ-(5-hydroxy-3-indolyl)-α-oxindolyl-γ-oxobutyric
acid (II). I (1 g.), 2 g. Zn dust, and 100 ml. 2N NaOH refluxed in N 45 min. gave 500-650 mg. II, needles, m. 252-4°
(decompn.) (from Me2CO-ligroine). In one expt. the evolved gas was collected in 2N HCl and converted to the p-
toluenesulfonamide, m. 136°. II (200 mg.) treated 15 min. with Et2O-CH2N2 gave 170 mg. of a Me ester (III), needles, m.
247-9°. III was also formed when 200 mg. II was heated with MeI and K2CO3 in Me2CO in 90 mg. yield. Addn. of
Me2SO4 (2.5 ml.) to 250 mg. II in 17 ml. 2N NaOH during 45 min. gare 250 mg. of the trimethyl deriv. (IV), plates, m. 266-
7° (decompn.) (from Me2CO). Methylation of 1 g. II in the presence of 30 ml. 2N NaOH with an excess of Me2SO4 so
that the mixt. eventually became acidic gave 900 mg. tetramethyl deriv. (V), needles, m. 181° (from alc.); 2,4-
dinitrophenylhydrazone, red prisms, m. 228-30° (decompn.). IV in refluxing Me2CO treated with MeI and K2CO3 gave V.
II (100 mg.), 4 ml. Ac2O, and 100 mg. NaOAc refluxed 15 min. and 12 hrs. later the product collected gave 30 mg. 4-(5-
acetoxy-1-acetyl-3-indolyl)-2-(1-acetyl-3-oxindolylidene)-4-hydroxybut-3-enoic lactone (VI), red needles, m. about 286°
(decompn.) (from C6H6). Acetylation by Ac2O-C5H5N 5 days at 0° gave an inseparable mixt. of red and colorless
products. IV (100 mg.), 100 mg. anhyd. NaOAc, and 3 ml. Ac2O refluxed 10 min. gave 30 mg. 4-hydroxy-4-(5-methoxy-
1-methyl-3-indolyl)-2-(1-methyl-3-oxindolylidene)but-3-enoic lactone (VII), magenta plates with a green reflex, m. 268-70°
(decompn.) (from C6H6). VII did not contain an acetyl residue. Under the same conditions V was recovered unchanged.
VII (880 mg.) in 1 l. refluxing Me2CO cooled rapidly and just before crystn. started 1.3 g. KMnO4 added gave a product
first sepd. by chromatography from C6H6 on talc., but more successfully by fractional sublimation in a high vacuum. This
procedure gave 1-methylisatin (VIII), m. 134° (from C6H6-ligroine), and 5-methoxy-1-methylisatin (IX), m. 175-6° (from
C6H6-ligroine). Extn. of the MnO2 ppt. with hot H2O gave 100 mg. of an acidic solid which was combined with Et2O
extractables and methylated with CH2N2 to give Me 5-methoxy-1-methyl-3-indolylglyoxylate (X), prisms, m. 133° (from
Me2CO-ligroine). VI (1 g.) in 1.2 l. Me2CO treated at 40° with 1 g. KMnO4 in 200 ml. Me2CO gave 82 mg. VIII and 71 mg.
IX. II (0.5 g.) and Cu bronze in 10 ml. glycerol heated 10 min. to 260-70° gave 60 mg. 5-hydroxyindole, needles, m. 106-
7°. The residue sublimed at 180°/0.001 mm. gave 15 mg. of a crystn. product as cubes, m. 265°; 2,4-
dinitrophenylhydrazone; acetyl deriv., m. 190°. IV (0.2 g.) heated 8 hrs. in 15 ml. alc. with 1 ml. 90% N2H4.H2O gave 200
mg. of a pyridazinone (XI), needles, m. 242° (from 95% alc.). XI was formed in a similar reaction with V. Et 5-
methylindole-2-carboxylate gave 5-methoxyindole-2-carboxylic acid which was decarboxylated to 5-methoxyindole (XII).
XII (0.7 g.) in 15 ml. Et2O treated with 0.75 ml. oxalyl chloride gave 1 g. 5-methoxy-3-indolylglyoxylyl chloride (XIII),
orange-red solid, m. 130°. XIII (0.5 g.) in 100 ml. 2N KOH was cooled and acidified gave 300 mg. 5-methoxy-3-
indolylglyoxylic acid (XIV), prisms, m. 248° (from EtOAc). XIV (0.3 g.) in 30 ml. Me2CO treated with 1.5 g. KOH in 4.5 ml.
H2O, then 2.5 ml. Me2SO4 added during 20 min., and the mixt. left 20 min. and sepd. gave 0.20 g. 5-methoxy-1-methyl-3-
indolylglyoxylic acid (XV), needles, m. 194° (from EtOAc). The Me2CO layer from the methylation mixt. afforded 0.075 g.
X. X was also obtained by the action of CH2N2 on XV or by evapn. of a soln. of XV in MeOH contg. a trace of concd.
HCl. XIII (0.5 g.) in 35 ml. Et2O and 4 ml. MeOH converted to 0.45 g. Me 5-methoxy-3-indolylglyoxylate (XVI), plates, m.
255° (from Me2CO). XVI (0.3 g.) with Me2SO4 in aq. Me2CO and KOH gave 0.23 g. X. 5-Methoxy-1-methylindole (1 g.)
and 1.5 ml. NCCO2Me in Et2O left 12 hrs. at 0-5° with HCl and the ketimine-HCl decompd. with warm dil. Na2CO3 gave
X. IX was prepd. by methylation of 5-methoxyisatin in 50% MeOH with 2.5 ml. Me2SO4 and sufficient 2N NaOH to
maintain neutrality, giving IX as dark red needles.
~12 Citings
212. Acylation of epoxy ester plasticizers

By Rowland, Stanley P.; White, Ralph G.
CAPLUS
The acylation of epoxy esters gives good plasticizers and stabilizers for vinyl resins, nitrocellulose, and chlorinated
rubber which show no tendency to migrate to the surface. On epoxylation of unsatd. fatty acid esters with performic or
peracetic acid, side reactions form hydroxyformyloxy or hydroxyacetoxy compds. These are converted to acetoxy,
propionyloxy, or butyryloxy-groups by the corresponding anhydrides, ketenes or free acids. To preserve the total epoxy
content, the mild acylation avoids high concns. of free acylating acid by use of great excess of acylating agents (300-
1000% calcd. on the basis of the convertible H), such as Ac2O, propionic and butyric anhydride, ketene, methyl ketene,
or ethyl ketene. The reaction is carried out at 100-50° for 4-1 hrs. The absence of H2O is favorable to recovery of the
acylating agent. An epoxy content of 80% of theory is desired. For epoxylated glyceryl esters, destructive acetylation is
used. The acetylation is performed in the presence of anhydride and free acid to split the oxirane ring. The reaction is
carried out with addn. of NaOAc at 130-170° for 2-12 hrs. and is stopped at an epoxy content of 15-20% of theory to
preserve the stabilizing properties. Epoxy products of all combinations of satd. and unsatd. alcs. and satd. and unsatd.
acids may be used. For example, 103 g. Ac2O and 400 g. 2-ethylhexyl epoxystearate (3.66% epoxy O, I no. 2.7, sapon.
no. 151, and acid no 2.7) were boiled for 4 hrs. First AcOH was distd. off and then Ac2O at 100° and 2 mm. The
reaction product had 3.56% epoxy O, I no. 2.5, sapon. no. 167, and acid no. 2.7. A 10 µ thick poly(vinyl chloride) film
with 40% plasticizer was produced and soaked for 24 hrs. in a 1% soln. of Ivory soap at 60°. The loss in wt. was detd.
The acetylated epoxy ester-contg. film was 25% more resistant to extn. The destructive acetylation was carried out with
epoxy soybean oil 200 (epoxy O 5.97%), Ac2O 300, and NaOAc 3 parts for 3 hrs. with reflux. The volatile components
were dist. off at 125° and 1 mm. The reaction product contained 3% epoxy O.
~1 Citing
213. 16α-Hydroxy-1,4-pregnadienes
By Bernstein, Seymour; Lenhard, Robert H.; Allen, Wm. S.
CAPLUS
Dehydrogenation of 4-pregnenes to the corresponding cryst. 1,4-pregnadienes is accomplished by microbiol,
fermentation with Corynebacterium simplex ATCC 6946 (Lederle No. 45) in a suitable nutrient medium. The new
compds. are useful as antiinflammatory agents and are used in combination with fillers and excipients and parenterally in
soln. or in suspension. Sterile Trypticase soy broth medium (100 ml.) inoculated with a cell suspension of C. simplex
incubated 8 hrs. at 37° with shaking, 25 portions of 100 ml. sterile Trypticase soy broth medium without glycerol
inoculated with 1 ml. of the above inoculum and incubated 40 hrs. at 32°, 40 mg. 4-pregnene-11β,16α,17α,21-tetrol-3,20-
dione in 4 ml. alc. added to each portion, the fermentation continued 8 hrs. at 32° the samples pooled, the mash (pH 8.1)
centrifuged, the beer extd. with 3 l. CH2Cl2 and 3 times with 2 l. CH2Cl2, the ext. (9 l.) washed with satd. brine, evapd. in
vacuo, the oily residue (509 mg.) in 1.5 ml. stationary phase (SP) from the system 3:2:2 petr. ether (b. 90-100°)-MeOH-
H2O treated with 3 g. diatomaceous earth, the paste packed onto a 35 × 1.5-cm. column contg. 25 g. diatomaceous earth
impregnated with 12.5 ml. SP, and the column eluted with the mobile phase of the solvent system gave 207 mg. solid
which, crystd. from Me2CO-petr. ether (b. 60-70°), yielded 1,4-pregnadiene-11β,16α,17α,21-tetrol-3,20-dione (I), m. 229-
31°, λ 241 mµ (ε 14,500, EtOH), ν 3412, 1718, 1667, 1622, 1098, 1072 cm.-1 (KBr); 16,21-diacetate, m. 161-3° (from
EtOAc-petr. ether, b. 90-100°), λ 242 mµ (ε 14,200, EtOH), ν 3458, 1758, 1668, 1632, 1612, 1234, 1060 cm.-1 Similarly,
dehydrogenation of 20 mg. 9α-fluoro-4-pregnene-11β,16α,-17α,21-tetrol-3,20-dione by microbiol. fermentation,
acetylation of the crude product, and control of the chromatographic sepn. by paper-strip chromatography yielded 13 mg.
9α-fluoro-1,4-pregnadiene-11β,16α,17α,21-tetrol-3,20-dione 16,21-acetate (II), m. 150-240° (from Me2CO-petr. ether), λ
239 mµ (ε 15,200, abs. alc.), 261, 308, 387 mµ (H2SO4); bis-(2,4-dinitrophenylhydrazone), λ 258, 300, 312, 400 mµ
(CHCl3). II (100 mg.) in 10 ml. MeOH at 0° (N atm.) treated with 35 mg. KOH in 2 ml. MeOH, the soln. kept 1 hr. at room
temp., neutralized with AcOH, evapd. (N atm.), H2O added to the solid product, the mixt. cooled, filtered, and the residue
washed with H2O, dried, and crystd. 3 times from Me2CO-petr. ether gave 29 mg. 9α-fluoro-1,4-pregnadiene-
11β,16α,17α,21-tetrol-3,20-dione, m. 260-2.5°.
~2 Citings
214. Steroid intermediates

By Johnson, Wm. S.; Kemp, Alexander D.; Pappo, Raphael
CAPLUS
1-Methoxy-8-oxo-10a-methyl-5,6,8,9,10,10a,11,12-octahydrochrysene (I) is used as starting material for syntheses in the
steroid field. I (20 g.) in 300 cc. dimethoxyethane with 5 l. anhyd. NH3 and 500 cc. alc. treated 2-3 min. with 11 g. Li wire,
21 g. Li added over 15-20 min., on disappearance of blue color the mixt. warmed to remove NH3, 1 l. Et2O added, 1.5-2.0
l. ice H2O added, the Et2O layer sepd., washed with H2O, dried, and evapd. Five similar runs were combined to yield
103 g. crude trans-anti-trans-1-methoxy-8β-hydroxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene
(II), m. 134-6° (Et2O). Crude II (80.3 g.) in 400 cc. isopropenyl acetate refluxed until complete soln., cooled, 4 g. p-
MeC6H4SO3H.H2O added, and left overnight at room temp. gave trans-anti-trans-1-methoxy-8β-acetoxy-10a-methyl-
4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (III), m. 151.2-2.3°, sublimed at 140°/0.0 7 mm., λ 271, 278 mµ,
log ε 3.15, 3.16. III (404.2 mg.), 668 mg. Pb(OAc)4, and 1 cc. AcOH heated 20 min., glycerine added to destroy excess
Pb(OAc)4, 1 cc. H2O added, the ppt. collected, washed with H2O, and chromatographed on Al2O3 gave trans-anti-trans-
1 - methoxy - 10a - methyl-8β, 12 - diacetoxy-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (IV), m. 205.5-
11.7° (alc.), λ 275,281 mµ, log ε 3.38, 3.378. III (39.4 g.) in 98 cc. AcOH heated 27 min. at about 100° with 64.5 g.
Pb(OAc)4, 300 cc. C6H6 added followed by Et2O, the crude product heated 14 hrs. at 100° under N with 600 cc. AcOH,
the solvent removed, and the process repeated gave trans-anti-trans-1-methoxy-8β-acetoxy- 10a - methyl -
4bβ,5,6,6a,7,8,9,10,10a,11bα-decahydrochrysene (V), m. 157.2 9.0°(alc.), sublimed at 152°/0.06 mm. The residue from
the above reaction in 55 cc. C6H6 mixed with 600 cc. 100% HCO2H pptd. some V. The mixt. cooled, 13.5 cc. 30% H2O2
added all at once, the mixt. left 28 min., the solvents removed, the remaining gum dissolved in C6H6-Et2O, washed with
H2O, 5% NaOH, 20% NaHCO3, and H2O, filtered, and evapd. gave the formate (VI) as a reddish brown gum. VI in 670
cc. alc. and 5 l. NH3 treated during 0.5 hr. with 70 g. Li, decompd., H2O added, extd. with Et2O, evapd., and purified gave
trans-anti-trans-1-methoxy-8β, 11β-dihydroxy-10a-methyl-4bβ,5,6,6aα,7,8,9,10,10a,10bα, 11,12-dodecahydrochrysene
(VII), m. 237-41° (MeCOEt). V (1.166 g.) in 20 cc. 100% HCO2H left at 17-22° with 0.41 cc. 30% H2O2 and samples
taken after the 2nd, 3rd, and 4th hr. showed the same absorption at 275 mµ with a shoulder at 283 mµ and min. at 250
mµ. After 4.33 hrs. the mixt. was worked up as above. Crude VI dissolved in 30 cc. alc. and poured into 300 cc. NH3,
8.4 g. Na added in 7 equal portions over 1 hr., and worked up gave crude product which was chromatographed on Florisil
to give 253 mg. carbinol, 120 mg. 8β,11α-diol, and 63 mg. VII. VII (6.95 g.) in 500 cc. tetrahydrofuran passed through
Florida fullers earth gave purified VII, m. 238-41°. VII (6.157 g., so purified) in 675cc. alc. added all at once to 1500 cc.
anhyd. NH3, 82 g. Li added during 2 hrs. (after 1 hr. the Li reacted very sluggishly and more alc. and NH3 added), the
NH3 removed, and the residue worked up gave after repeated crystn. dl-D-homo-18-nor-11β-hydroxy-13,14-
dehydroepiandrosterone (VIII), m. 276-7° (alc.), λ 247.8 mµ, ε 12,430, and 164 mg. dl-D-homo-18-nor-11β-hydroxy-
16,17-dehydroepiandrosterone (IX), m. 214-34° (MeCOEt), λ 225 mµ; diacetate m. 204-5° (alc.). VIII (3.174 g.) in 560
cc. 95% alc. hydrogenated 1 hr. at 46 lb./sq. in. with 360 mg. KOH in 1 cc. H2O and 1 g. 10% Pd-C, the soln. filtered, the
filtrate concd., and left overnight with a slight excess AcOH gave dl-D-homo-18-nor-11β-hydroxyepiandrosterone (X), m.
256-7°(MeCOEt). IX diacetate (10 mg.) similarly reduced gave X diacetate, m. 158-9° identical with the specimen
obtained by acetylation of X. Conversion of X to the 17-furfurylidene deriv. (diacetate m. 246-8°) followed by angular
methylation of C-13 and acetylation gave dl-3β,11β-diacetoxy-17-furfurylidene-D-homoandrostan-17a-one, m. 256-8°,
along with the 13-iso isomer, m. 242-3°. These compds. were ozonized and the resulting dibasic acids esterified with
CH2N2 to give, resp., dl-di-Me 3β, 11β-diacetoxyetioallohomobilianate, m. 131.5-3.0°, and 13-iso compd., m. 143.5-4.5°.
Cyclization of the DL-esters with KOCMe3, followed by hydrolysis and decarboxylation, accomplished by heating with aq.
dioxane at 200-10° gave after sapon. dl-3β,11β-dihydroxyan-drostan-17-one, m. 249-51.5°, and the 13-iso isomer, m.
216-17°. The diacetate of the 1st compd. m. 217-17.5°. trans-syn-cis-1-Methoxy-8β-acetoxy-10a-methyl-
4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (1.050 g.), m. 130-2°, and 2.10 g. Pb(OAc)4 in 1 ml. AcOH
heated 35 min. gave trans-syn-cis-1-methoxy-8β,12-diacetoxy-10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-
dodecahydrochrysene (XI), m. 187-9° (alc.) (decompn.), λ 275 mµ, log ε 3.44. XI in AcOH heated 2 hrs. at 120° gave
trans-syn-cis-1-methoxy-8β-acetoxy-10a-methyl-4b,5,6,7a,7,8,9,10,10a,10b-decahydrochrysene (XII), m. 143.5-4.5°, λ
269, 298, 309, mµ, log ε 4.01, 3.75, 3.71. Sometimes a different polymorphic form was obtained which m. 120-1°,
resolidified, and m. 137-40°. XII (0.2 g.) in 2 ml. CHCl3 left 25 hrs. at 0° with 1.4 ml. BzO2H in C6H6 and the product
chromatographed on Florisil gave 0.087 g. trans-anti-cis-1-methoxy-8β-acetoxy-11-hydroxy-12-benzoxy-10a-methyl-
4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene, prisms, m. 198-200° (alc.), λ 226, 274, 281 mµ, log ε 4.31,
3.58, 3.56. The cis-anti-trans-carbinol (9.96 g.) on acetylation gave cis-anti-trans-1-methoxy-8α-acetoxy-10a-methyl-
4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (XIII), m. 107-12°. XIII (20 g.) in 50 ml. AcOH heated 15 min. at
95-110° with 34 g. Pb(OAc)4 gave cis-anti-trans-1-methoxy-8α,12α-diacetoxy-10a-methyl-
4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (XIV). XIV in 300 ml. AcOH heated 17 hrs. at 93-5° under N,
concd. to 80 ml., cooled to room temp., and the product collected gave 13.89 g. cis-anti-trans-1-methoxy-8α-acetoxy-
10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b-decahydrochrysene (XV), m. 145-6°. XV (126.3 g.) in 600 ml. C6H6 left 50 hrs. at
6° with 1100 ml. 0.393M BzO2H in C6H6 gave 175 g. cis-anti-trans-1-methoxy-8α-acetoxy-11-hydroxy-12-benzoyloxy-
10a-methyl-4b,5,6,6a,7,8,9,10,10a,10b,11,12-dodecahydrochrysene (XVI), λ 223, 272, and 278 mµ. Crude XVI (66.3 g.)
in 1.8 l. alc. and 3.6 l. NH3 treated 1.5-2.0 hrs. with 85 g. Li wire, the NH3 removed, 2 l. ice H2O added, the mixt. extd.
with C6H6, and the combined exts. concd. gave the enol ether, m. 193-4°. Crude enol ether (41.48 g.) in 1.2 l. alc. contg.
300 ml. H2O and 75 ml. concd. HCl refluxed 1 hr. under N, the soln. concd. to 200 ml., extd. with CHCl3, the combined
exts. dried, and concd. gave cis-anti-trans-1-oxo-8α,11α-dihydroxy-10a-methyl-1,2,3,4,4b,5,6,6a,7,8,9,10,10a,10b,11,12-
hexadecahydrochrysene (XVII), m. 227.0-7.5°, λ 248 mµ. The lower m.p. of the 2nd crop was due in part to the
presence of cis-anti-trans-1-oxo-8α,11a-dihydroxy-10a-methyl-1,4,4a,4b,5,6,6a,7,8,9,10,10a,10b,11,12,12a-
hexadecahydrochrysene (XVIII). Crude XVI (3.02 g.) similarly treated gave 470 mg. XVII, m. 211-16° (Me2CO). Mixed
XVII and XVIII (41.50 g.) in 400 ml. alc. contg. 10 ml. 10% KOH and 3 ml. 10% Pd-C absorbed 0.14 mole H at 50 lb./sq.
in. during 35 min. to give cis-anti-trans-1-oxo-8α,11a-dihydroxy-10a-methyloctadecahydrochrysene, m. 184-5° (EtOAc-
Et2O). The compds. listed above having an OH group in the 8 position may be used in the free alc. form or in the form of
esters.
~1 Citing
215. Some reactions of the 1,3-O-benzylideneglyceritols

By Baggett, N.; Foster, A. B.; Stacey, M.
From Chemistry & Industry (London, United Kingdom) (1958), 1229-30. Language: Unavailable, Database: CAPLUS
cf. preceding abstr. The cis isomer (I) of 1,3-O-benzylideneglyceritol (m. 83-4°) may readily be isolated pure by fractional
crystn. of the reaction mixt. from BzH and glyceritol, but the trans isomer (II), m. 64-5°, cannot be so obtained. II was first
obtained as the acetate (m. 115-16°) by treatment of the mixt., after removal of I, with pyridine-Ac2O. Sapon. of the
acetate yielded pure II. The cis and trans forms may be sepd. by chromatography on alumina. I and II were converted to
a mixt. of both forms (in which the cis form predominated) by treatment with (iso-PrO)3Al. Acetylation of I gave a single
acetate (III), m. 100-1°; under the same conditions II gave a mixt. of III and an acetate (IV), m. 115-16°. The acetates
were sepd. by chromatography and were, resp., the acetates of I and II. Benzylation of I by treatment of its benzene
soln. with Na, NaH, or NaNH2 followed by benzyl bromide gave a chromatographically homogeneous O-benzyl ether, m.
75-6°. Under the same conditions, II gave a mixt. of O-benzyl ethers, m. 91-2°, which were sepd. on alumina. Acid
hydrolysis of the ethers gave 2-O-benzylglyceritol in each case. It seemed probable that these ethers are cis- and trans-
2-O-benzyl-1,3-O-benzylideneglyceritol. The sensitivity of II to isomerization under relatively mild chem. conditions is
shown.
~0 Citings
216. Orcein dyes. VIII. The constitution of the hydroxyorceins and their oxidation products
By Musso, Hans; Kramer, Horst
cf. C.A. 52, 18306b. α-Hydroxyorcein (I) possesses the tautomeric structures Ia and Ib (R = H), while β-and γ-
hydroxyorcein have the structures II and III, resp. Oxidation of II and III gave the minor orcein (IV) components IIa and
IIb as well as IIIa and IIIb formed by the oxidation of one and then of the 2nd 2,4,6-Me(HO)2C6H2 group to the
hydroxytoluquinonyl group, resp. IV (18.4 g.) subjected to a partition chromatography with BuOH-0.2M phosphate buffer
on cellulose at pH 12.00 gave 1.271 g. I, 2.800 g. II, 1.645 g. III, 1.542 g. IIIa, and 0.910 g. IIIb. The fractions II, III, IIIa,
and IIIb sepd. again at pH 11.50 yielded 0.528 g. II, 0.490 g. IIa, 0.308 g. III, 1.610 g. IIIa, and 0.730 g. IIIb. The main
components II and III chromatographed finally on silica gel with 4:4:1 CHCl3-HCONH2-pyridine yielded 0.220 g. cryst. II
and 0.182 g. cryst. III. IIa, IIIa, and IIIb subjected again to a partition chromatography gave 0.039, 0.192, and 0.102 g.
homogeneous, amorphous products, resp. I (90.1 mg.) in 1 cc. pyridine treated at 20° with 2 drops Ac2O, evapd. after 20
hrs. in vacuo, evapd. 3 times with a little C6H6 in vacuo, chromatographed on CaSO4, and fractionally crystd. from C6H6
gave 43.1 mg. acetate (V) of Ib, orange prisms, which lost at 100° in vacuo 1 mole C6H6 of crystn., m. 189-91° with
sintering at 180° (decompn.); the mother liquors evapd. and the residue recrystd. from C6H6-cyclohexane yielded 20.0
mg. acetate (VI) of Ia, orange-yellow rods, m. 211° (decompn.). In similar runs with impure I or after longer storage of the
reaction mixts. up to 17% of a N-free, cryst. product (presumably an acetate of a degradation product of I), m. 177.5-79°
(C6H6), was also obtained. V (27.6 mg.), 100 mg. Zn dust, 20 mg. NaOAc, and 1.5 cc. Ac2O refluxed 45 min., cooled,
filtered, evapd. in vacuo, and the residue chromatographed from C6H6 on CaSO4 yielded 6.3 mg. leuco-acetate (VII) of I,
m. 210-12° (decompn.) (C6H6-cyclohexane). V (45.7 mg.) in 3.5 cc. Ac2O hydrogenated at 25° over 58.2 mg. 5% Pd-
BaSO4 during 20 min., treated under H with 2 cc. pyridine, filtered after 3 hrs., evapd. in vacuo, and the residue recrystd.
from C6H6 yielded 21 mg. VII, leaflets, m. 207-9° (decompn.). The II from the chromatography on silica gel recrystd. from
MeOH gave 165 mg. pure II, red needles, decomp. with effervescence when placed on the block at 340°. II (70 mg.)
treated 10 min. at 20° with pyridine-Ac2O and chromatographed with CHCl3 and CHCl3-EtOAc (7:3) yielded 85 mg.
acetate (VIII) of II, orange-yellow crystals, m. 140.5-41° with sintering at 132° (decompn.); it loses 1 mole PhMe in vacuo
at 100°. VIII (57.1 mg.) reduced with Zn dust in the usual manner yielded 25.3 mg. leuco-acetate, m. 130-4° (decompn.).
III (obtained from the chromatography on silica gel) (182 mg.) recrystd. from 10 cc. MeOH with the addn. of a few drops
H2O gave 34.7 mg. red-brown rodlets and plates; the mother liquor concd. in vacuo gave an addnl. 145 mg. less pure III;
pure III turned black from 250° without melting and decompd. with effervescence when placed on the block at 330°. III
(120 mg.) treated with pyridine-Ac2O gave 170 mg. acetate (IX), orange-yellow needles, m. 143-7° with sintering at 132°
(decompn.). II (or III) heated 1 hr. at 200° gave a mixt. of 1:1 II-III. IIa, IIb, IIIa, and IIIb decompd. completely when
heated in glycerol. IIIa and IIIb were obtained as red-brown, amorphus powders, turning black at 250-300°, after
purification by partition chromatography. IIIa (66.8 mg.) treated with Ac2O-pyridine, chromatographed, and dried at 100°
yielded 59.0 mg. acetate, orange powder, m. 96-101°. IIIb (49.5 mg.) gave similarly 57.7 mg. acetate of IIIb, m. 119-22°.
The R values (in reference to I = 1.00) were detd. on cellulose powder columns with BuOH-0.2M phosphate buffer at 17°
and pH 12.25, 12.00, 11.75, and 11.50: II, 0.10, 0.22, 0.31, 0.47; IIa, 0.07, 0.14, 0.18, 0.19; IIb, 0.035, 0.05, 0.08, 0.08;
III, 0.05, 0.11, 0.16, 0.28; IIIa, 0.035, 0.07, 0.08, 0.11; IIIb, 0.03, 0.03, 0.03, 0.03; phenazine (Xa) of IIIa, -, 0.62, 0.65, -;
phenazine (Xb) of IIIb, -, 1.23, 1.11, -. Crude III (290 mg.) in 10 cc. 0.2M phosphate buffer (pH 11.6) and 10 cc. BuOH
shaken 5 min. with 150 mg. K nitrosodisulfonate, acidified with dil. H2SO4, the BuOH phase washed with H2O and evapd.
in vacuo, the residue dissolved in 50 cc. glacial AcOH, the soln. boiled briefly with 120 mg. ο-C6H4(NH2)2, partitioned
after 12 hrs. between H2O and BuOH, the org. phase washed with H2O and evapd. in vacuo, the residue
chromatographed with BuOH-phosphate buffer (pH 11.75), and the 3 red-violet zones eluted and evapd. gave 39 mg. Xb,
RI 1.11, 105 mg. Xa, RI 0.65, and a few mg. substance which treated with ο-C6H4(NH2)2 gave Xb; the crude Xa
chromatographed on cellulose powder with 2:2:9:5:5 BuOH-glacial AcOH-Me2CO-Bu2O-H2O yielded 60 mg. dark red
lacquer; a 17-mg. portion in 1 cc. pyridine and 0.5 cc. Ac2O evapd. after 10 min. in vacuo, the residue chromatographed
with 7:3 CHCl3-EtOAc on silica gel, the eluate evapd., and the residue (15 mg.) recrystd. from a drop C6H6 gave acetate
of Xa, m. 275-80°, turning dark-brown at 263-5°. Pure III (60 mg.) oxidized in the usual manner with 220 mg. K
nitrosodisulfonate and the product treated with ο-C6H4(NH2)2 and chromatographed gave 75 mg. Xb, dark red lacquer; a
67-mg. portion acetylated and chromatographed twice on silica gel yielded 32 mg. orange cryst. residue which recrystd.
from 2 cc. abs. EtOH gave 21 mg. acetate of Xb, m. 214-16° with previous sintering; 5 mg. 2nd crop. The infrared
absorption spectra of the acetates of III, IIIa, IIIb, 7-acetamido-4,5-dimethyl-2-phenoxazone (XI) 7-AcO analog (XII) of XI,
the acetates of Ia and Ib, II, and α- and β-aminoörcein, and the ultraviolet absorption spectra and visible spectra of XII,
the acetates of Ia, Ib, II, Xa, and Xb, and 3-acetoxy-1-methylphenazine are recorded.
~3 Citings
217. Detection of organic impurities in glycerol by paper chromatography

By Grynberg, Halina; Jarnuszkiewicz, Hanna; Malinowska, Irena
From Prace Inst. i Lab. Badawczych Przemslu Spozywczego (1958), 8(No. 3), 15-30. Language: Unavailable,
Database: CAPLUS
NH4 salts of C1-C6 aliphatic acids were sepd. by descending chromatography on Whatman No. 1 paper in an atm. NH3
and BuOH with BuOH satd. with NH4OH soln. as an eluant and bromcresol green as a developer. Rf values, relative to
NH4 butyrate were: formate and acetate 0.45; propionate 0.70; butyrate 1.0; valerate 1.27; and caprylate 1.54 (averages
for 17 runs). Chromatograms of 10-20 microliters glycerol (I) run alongside synthetic blanks permitted rough quant.
estns. Crude I contained 1-2% and distd. I 0.2-0.7% of these acids. Descending chromatography of 5 microliters of I
with PhOH, equilibrated with a phosphate buffer of pH 12 as an eluant, Whatman No. 1 paper, an atm. of Ph/phosphate
buffer, and ninhydrin developer demonstrated the presence of aspartic acid, glutamic acid (II), serine (III), glycine (IV),
threonine (V), and alanine (VI). Similarly, with BuOH/glacial AcOH/water system, cystine, lysine, histidine, arginine,
asparagine, IV, III, V, II, VI, proline, tyrosine, valine, and methionine were sepd. in the order given. Total amt. of amino
acids in crude I was estd. to be 0.14% and in distd. I 0.06-0.08%. Detection of aldehydes in I was carried out by pptg.
the corresponding 2,4-dinitrophenylhydrazones, dissolving them in pyridine: MeOH: PhOH soln. (1:10:5) and
chromatographing at 40° on acetylated Whatman No. 1 paper with EtOH as an eluant. The following were detected: (Rf
range for 25 runs) glyceraldehyde (0.18-0.22); acrolein (0.40-0.51); and formaldehyde (0.58-0.72). The presence of I did
not interfere with chromatography of the compds. investigated.
~0 Citings
218. 16-Oxygenated steroidal compounds

By Fried, Josef; Perlman, David; Langlykke, Asger F.; Titus, Elwood O.
CAPLUS
16α-Hydroxy steroid derivs. were prepd. from 3,20-dioxo steroids of the pregnane series by microbiol. oxidn. by
Streptomyces argenteolus ATCC 11,009 (I), S. roseochromogenus (Waksman No. 3689) (II), S. viridis (Waksman No.
3690) (III), S. olivaceus (Waksman No. 3688) (IV), the molds Pestalotia funerea (V), Aspergillus nidulans (VI), and A.
niger (VII), and by Oppenauer oxidn. Thus oxidn. of progesterone by I-V yielded: 16α-hydroxyprogesterone (VIII), m.
225-6°, [α]23 D 158° (c 0.38, CHCl3), λ 239 mµ (alc.) (ε 17,000), 3.04, 5.90, 6.05, and 6.20 µ (Nujol); 16α-
hydroxypregnane-3,20-dione, m. 199-200°, [α]23 D 90.5° (c 0.82, CHCl3), and dihydroxyprogesterone, m. 215.5-16.5°,
[α]24 D -39° (CHCl3), λ 243 mµ (alc.) (ε 14,400). Acetylation of VIII with Ac2O and C5H5N gave the monoacetate, m. 134-
5°, [α]22 D 107°. Oxidn. of compd. S acetate with I yielded the hydroxy deriv., m. 224-7°, which when acetylated m. 209-
11°, [α]25 D -58° (0.53%, CHCl3). Oxidn. of deoxycorticosterone acetate by I-IV gave 16α-hydroxy-11-
deoxycorticosterone (IX), m. 202-3°, [α]23 D 130° (c 0.40, CHCl3), λ 239 (ε 18,700) and 290 mµ (ε 148) (alc.), 291 and
298 mµ, 5.80, 6.04, and 6.07 µ (Nujol), and 4,5-dihydro-16α-hydroxy-11-deoxycorticosterone (X), m. 215-7°, [α]23 D 44°
(c 0.23, CHCl3), λ 2.98 and 5.88 µ (Nujol). Treatment of IX with Ac2O and C5H5N gave the 21-monoacetate, m. 206-
8.5°, [α]D 112° (c 0.31, CHCl3), λ 239 mµ (ε 18,200) (EtOH), and the diacetate, m. 151-3°, [α]23 D 105° (c 0.46, CHCl3).
Treatment of X with Ac2O and C5H5N gave the acetate, m. 130-2°, [α]23 D 55° (c 0.36, CHCl3). Oxidn. of 4-androstene-
3,17-dione by I-IV yielded 16α-hydroxy-4-androstene-3,17-dione (XI), m. 185-7°, [α]D 194° (c 0.42, CHCl3), λ 239 (ε
17,000) and 300 mµ (ε 145) (alc.), 3.01, 5.72, 6.08, and 6.22 µ (Nujol), pos. Tollens test, pos. reaction with 2,4,5-
triphenyltetrazolium chloride in MeOH-KOH; monoacetate m. 177-80°, [α]D 137° (c 0.39, CHCl3); diacetate m. 151-3°,
[α]23 D 105° (c 0.46, CHCl3). Oxidn. of testosterone by II-V gave 16α-hydroxytestosterone, m. 183-4°, [α]23 D 76° (c 0.59,
CHCl3). IX (166 mg.) and 2 mL. dry C5H5N at 5° treated with 80 mg. BzCl (1:1 equiv.) in 2 mL. CHCl3, kept overnight in
an icebox, dild. with ice, CHCl3, washed with dil. HCl, NaHCO3, and H2O, evapd. in vacuo, dissolved in 10 mL. dioxane
and 200 mg. HIO4.2H2O in 2 mL. H2O, kept overnight, treated with a few drops of glycerin, shaken with 40 mL. CHCl3,
the CHCl3-dioxane layer extd. with satd. NaHCO3 soln., washed with H2O, dried over Na2SO4 and in vacuo, and
recrystd. from Me2CO-Et2O gave 21-monobenzoate of IX, m. 210-2°, [α]D 129° (c 0.325, CHCl3), λ 290 mµ, 5.78, 5.82,
6.06, 6.23, 6.33, and 14.04 µ (Nujol). Oxidn. of VIII by VI yielded 6β,16α-dihydroxyprogesterone (XII), m. 230-2°, [α]24 D
75° (c 1.0, CHCl3), λ 235 mµ (ε 10,800) (alc.), 2.91, 5.90, 5.95, 6.00, 6.04, and 6.16 µ (Nujol). Oppenauer oxidn. of XII in
PhMe and cyclohexane yielded 16-allopregene-3,6,20-trione (XIII), m. 204-11°, [α]24 D 33° (c 0.65, CHCl3), λ 237 mµ (ε
9,500) (alc.). Hydrogenation of XIII with Pd-black in AcOH followed by oxidn. with CrO3 gave allopregnane-3,6,20-trione,
m. 223-8°. Oxidn. of VIII with VII gave 11α,16α-dihydroxyprogesterone (XIV), m. 213-5°, [α]23 D 128° (c 1.03, CHCl3), λ
240 mµ (ε 14,000)(alc.), 2.98, 5.86, 6.02, and 6.19 µ (Nujol). Oppenauer oxidn. of XIV in PhMe gave 11α-hydroxy-16-
dehydroprogesterone (XV), m. 169-74°, [α]24 D 138° (c 0.56, CHCl3), λ 239 mµ (ε 21,900) (alc.). Oxidn. of XV with CrO3
in AcOH yielded from Me2CO-C6H14 4,16-pregnadiene-3,11,20-trione (XVI), m. 179-83°, [α]24 D 246° (c 0.85 CHCl3), λ
235 mµ (ε 21,800) (alc.). Hydrogenation of XVI gave pregnane-3,11,20-trione. 16α-Hydroxyandrostenedione (60 mg.)
and 2 mL. pure dioxane treated with 60 mg. HIO4.2H2O in 0.5 mL. H2O and worked up in the usual way, oxidized with
CrO3 in AcOH, esterified with diazomethane in Et2O, chromatographed on Al2O3 (pH 4.5), and eluted with C6H6C6H14
and C6H6 gave di-Me-3-oxoetio-4-bilienate (di-Me 3-oxo-16,17-seco-4-androstene-16,17-dioate) XVII, m. 97-9°, [α]D 27°
(c 0.34, CHCl3), λ 239 (ε 17,580) and 315 mµ (ε 92) (EtOH). Oppenauer oxidn. of di-Me 3β-hydroxy-5-etiobilienate
yielded XVII, m. 100-1°, [α]23 D 26° (c 0.78, CHCl3), λ 238 mµ (ε 16,500) (alc.), 5.79, 6.03, and 6.20 µ (Nujol). Cf. C.A.
53, 3292c.
~0 Citings

219. Transformation of Reichstein's substance S to prednisolone by Pseudomonas
By Takeda, Rokuro; Nakanishi, Itaru; Terumichi, Jiro; Uchida, Minoru; Katsumata, Michio; Uchibayashi, Masao; Nawa,
Hayao
From Tetrahedron Letters (1959), (No. 18), 17-19. Language: Unavailable, Database: CAPLUS, DOI:10.1016/S0040-
4039(01)99995-2
cf. C.A. 52, 5340i. Both 1-dehydrogenation and 11β-hydroxylation can be induced simultaneously in the same mol. of a
substrate under appropriate conditions for enzyme formation by Pseudomonas and steroid transformation.
Pseudomonas sp. 109 (similar to P. boreopolis) irradiated 1-5 min. with a 30 w. ultraviolet ray lamp at 54 cm. distance
and incubated on a bouillon agar plate contg. 0.1% Reichstein's substance S (I), the bioconversion products examd. by
paper chromatography and sepd. gave a mutant (II) showing excellent ability in formation of prednisolone (III). II
incubated in a medium contg. corn steep liquor, phosphates, sulfates, glycerol, and urea and filtered after carefully
observed fermentation (loc. cit.), the filtrate extd. with EtOAc and the ext. concd., the product acetylated with Ac2O-
C5H5N and chromatographed on Florisil, eluted with Et2O-Me2CO, and the fractions isolated gave I acetate and 20-30%
III acetate, 21-acetoxy-1,4-pregnadiene-11β,17α-diol-3,20-dione, m. 230°, ν 3344, 3257, 1742, 1718, 1647, 1587, 1222
cm.-1 It is of interest that this one-step prepn. of therapeutically valuable III from I was conducted by microörganisms.
~0 Citings
220. The chemical structure of the phosphatide of the Calmette-Guerin bacillus

By Vilkas, Erna
cf. C.A. 52, 1362b. Further study of the bacillus Calmette-Guerin phosphatide (I) showed that it contains stearic, palmitic,
palmitoleic, octadecenoic, and tuberculostearic acids. Hydrolysis of I with 2N HCl for 20 min. at 98° gave a diglyceride;
glycerol was the only H2O-sol. product obtained on sapon. of this diglyceride. Complete methylation of the water-sol.
fraction obtained on hydrolysis of I established (paper chromatography) the presence of a trimethyl mannose and a
tetramethyl mannose. The glycoside bond between mannose groups is thought to be 1-4 or 1-6. Study of I from bacteria
grown on peptone-glycerol media revealed that it contained glucose as well as mannose. Acetylation of the water-sol.
fraction obtained on sapon. of I gave the following substances: triacetin; inositol hexaacetate; an acetate, m. 78-80° (m.
101-4°, after heating 4 hrs. in vacuum), [α]21 D 125°, contg. 5 glucose and 1 mannose per inositol residue; an acetate, m.
178-80°, [α]21 D 20.5°, contg. 1 mannose per inositol residue and an acetate, m. 135-6°, [α]20 D 54°, an inositol
dimannoside.
~0 Citings
221. Ring D steroid oximes and the Beckmann rearrangement

By Heard, R. D. H.; Ryan, Michael T.; Bolker, H. I.
DOI:10.1021/jo01084a006
Whereas simple ring D and ring A steroid oximes yielded the corresponding oxime acetates on subjection to mild
acetylating conditions, 3β-hydroxyandrostane-16,17-dione 16-oxime (I) gave a pure cryst. compd. which was
characterized by its chem. properties and behavior as an intermediate in a Beckmann rearrangement. Rearrangement
could be completed under appropriate, though equally mild, conditions. Reasons for the unexpected rearrangement
under such mild conditions are advanced. I purified by dissolving 2.95 g. crude product in 40 ml. MeOH and 10 ml. H2O,
refluxing with C, and concg. gave 70% I, m. 220°, λ 240 mµ, ε 9570. I(100 mg.) in 1 ml. C5H5N and 1 ml. Ac2O left
overnight gave 102 mg. C23H33O5N (II), m. 163-5° (Et2O), λ 223 mµ, ε 9431, stable in the dark, turned yellow within 1
week when exposed to light, and unstable in alc. (223 mµ peak disappeared). The structure of II corresponded to that of
an intermediate in the Beckmann rearrangement of I. Oximes were prepd. in the usual way by refluxing in alc. for 2 hrs.
in the presence of excess NH2OH.HCl and NaOAc. Acetylating conditions identical to those used in prepg. II were used
and the authenticity of the acetates was established by alk. hydrolysis to the starting oximes. 17-Oximino-3β-
acetoxyandrostane, m. 184-6°, gave 17-acetoximino-3β-acetoxyandrostane, m. 180-0.5°; cholestanone oxime, m. 200-
1°, gave 3-acetoximinocholestane, m. 124-38°; testosterone oxime, m. 222-3°, gave 17β-acetoxy-3-acetoximino-4-
androstene. II(0.5 g.)in 50 ml. 95% alc. was refluxed and samples were drawn at 1 hr. intervals and after the appropriate
diln. measured in the spectrophotometer at 223 mµ. The ε value change with time was as follows (time in hrs. and ε
value given): 0, 9400; 1, 1410; 3, 427; 4,427. After 6 hrs. an oil (III) was obtained; it was insol. in aq. Na2CO3 and could
not be extd. from an Et2O soln. with alkali. III (0.5 g.) in 50 ml. alc. refluxed 20 hrs. with 2.5 g. KOH gave a mixt. of 3β-
hydroxy-16,17-secoandrostan-16,17-dioic imide(IV)and 3β-hydroxy-16,17-seco-16,17-dioic acid 17-amide (V). CHCl3
(60 ml.) added to the acidified aq. suspension dissolved IV; the suspension filtered, and the ppt. collected and dried gave
220 mg. V, m. 218.5-20.5°. V dissolved in cold AcOH and treated with NaNO2 gave no evolution of N, which confirmed
the tertiary nature of the amide group. The CHCl3 soln. gave 113 mg. IV, m. 180-2.5° (MeOH-H2O). IV refluxed 24 hrs.
in 10% aq. KOH gave V. V (40 mg.) heated gradually to 200° with 5 ml. 20% KOH in glycerol gave a copious evolution of
N. The heating stopped after 2.5 hrs., the mixt. dild. with H2O, acidified, and left 2 hrs., and the solid filtered off and
washed gave 20 mg. II.
~4 Citings
222. Preparation of complex esters of 1-alkoxy-2,3-propanediol

By Malinovskii, M. S.; Vvedenskii, V. M.
From Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation) (1959), 32, 1610-13. Language: Unavailable,
Database: CAPLUS
Complex esters, R'CO2CH2CH(OH)CH2OR'' (I), were prepd. by acetylation of α-monoesters of glycerol in the presence
of 85% H3PO4. Mixing 37 g. monobutyl glyceride and 15 g. glacial AcOH with 30 ml. CCl4, adding 1.5 g. 85% H3PO4,
heating 3 hrs. on a H2O bath, distg. CCl4 and distg. the residue in vacuo yielded 92.3% 1-butoxy-3-acetoxy-2-propanol,
b6 102°, d20 1.0400, n20 D 1.440. The following I were similarly prepd. (R', R'', b.p., d20, n20 D, and % yield given); Me, Et,
91°, 1.0683, 1.4372, -; Me, CHMe2, 92°/5, 1.0621, 1.4358, 69.4; Me, CH2CHMe2, 102°/5, 1.0267, 1.4388, 83.7; Me,
CH2CH2CHMe2, 101°/4, 1.0186, 1.4374, 53.3; Me, CH2CH:CH2, 97°/5, 1.0709, 1.4468, 72.1; Et, Et, 98-100°/5, 1.0352,
1.4408, 71.8; Et, Bu, 104°/5, 1.0287, 1.4438, 48.6; Et, CH2CH2Me2, 102°/4, 1.0096, 1.4445, 51.8; Pr, Et, 105°/7, 1.0364,
1.4888, 80.5; Pr, Bu, 107°/5, 1.0082, 1.4468, 52.5; Pr, CH2CH2CHMe2, 112°/5, 1.0011, 1.4474, 32.8; C17H35, Et, -, -, -, -
(m. 49°); C17H35, Bu, -, -, -, - (m. 50-1°); C17H35, CH2CHMe2, -, -, -, - (m. 50°).
~0 Citings
223. Preparation and antifungal action of a series of 6-quinolyl sulfides and sulfones
By Gialdi, F.; Ponci, R.; Baruffini, A.
From Farmaco, Edizione Scientifica (1959), 14, 288-303. Language: Unavailable, Database: CAPLUS
Adding to 8 g. 6-mercaptoquinoline in 30 cc. EtOH and 2 g. NaOH in 8 cc. H2O in an N stream dropwise 7 g. MeI in 20
cc. EtOH, refluxing during the exothermic reaction, adding after 30 min. and cooling 80 cc. ice water, extg. with Et2O,
washing the ext., drying, evapg. and keeping the residue on ice gave 88% methyl 6-quinolyl sulfide (I), m. 47-9° (petr.
ether). Oxidn. of I with CrO3 (as described for III) at 85-90° gave 85% methyl 6-quinolyl sulfone, m. 130-2° (80% EtOH).
Adding to 8 g. 6-mercaptoquinoline in 30 cc. EtOH and 7.5 g. BuBr in 15 cc. H2O, heating on steam in an N stream,
adding dropwise 1.15 g. Na in 15 cc. EtOH, refluxing 30 min. longer, cooling, adding 80 cc. ice water, extg. with Et2O,
washing, drying, evapg. and distg. at 174°/2.5 mm. gave 70% butyl 6-quinolyl sulfide (II). Heating 2.5 g. II in 25 cc.
AcOH to 55-60°, adding dropwise during 1 hr. 2 g. CrO3 in 14 cc. AcOH dild. 1:1, increasing the temp. with stirring to 90°,
keeping at 90° for 9 hrs., dilg. after cooling with 6 vols. H2O and keeping 24 hrs. gave a ppt. of 78% butyl 6-quinolyl
sulfone (III), m. 76-8° (75% EtOH). The method used for II gave 70% amyl 6-quinolyl sulfide (IV), m. 48-50° (dil. EtOH,
2:1). Oxidn. as used for III gave during 7 hrs. at 95° 70% amyl 6-quinolyl sulfone, m. 94-5° (75% EtOH). Hexyl 6-quinolyl
sulfide (V), m. 45-7° (75% EtOH), was prepd. in 65% yield. The corresponding sulfone, m. 77-8° (Et2O-petr. ether), was
prepd. in 75% yield. Prepd. as described for II was 78% n-dodecyl 6-quinolyl sulfide (VI), m. 52-5° (EtOH), 68% n-
hexadecyl 6-quinolyl sulfide (VII), m. 70-2.5° (80% EtOH and ligroine), and with methylene iodide 75% bis(6-
quinolylthio)methane (VIII) m. 117-18° (C6H6 and EtOH-Et2O). p-Acetamidodiphenyl sulfide, m. 149-50° (prepd. by
catalytc reduction of p-nitrodiphenyl sulfide and acetylation) (10 g.) in 80 cc. AcOH and 10 g. CrO3 in 20 cc. H2O, heated
at 100° 5 hrs., dild. with 250 cc. H2O, and the solid filtered off and washed gave 94% p-acetamidodiphenyl sulfone, m.
195° (EtOH). Refluxing 10 g. of this compd. 3 hrs. with 100 cc. HCl, dilg. with 100 cc. hot H2O and neutralizing with 15%
NaOH gave 93% p-aminodiphenyl sulfone, m. 176° (EtOH). Mixing 30 g. p-aminodiphenyl sulfide, m. 96-9° (prepd. by
catalytic redn. of the corresponding NO2 deriv.), with 55.2 g. glycerol, and 25.5 g. AS2O5, adding slowly 50 g. H2SO4,
heating gradually with refluxing to 140°, then to 160°, refluxing 5 hrs., neutralizing to 75% with the calcd. amt. NaOH,
boiling with C, filtering, neutralizing with 10% NaOH, extg. with Et2O, washing the ext. with H2O, treating with C, extg.
with dil. HCl, treating the acid soln. with C, filtering, reëxtg. with Et2O, drying the ext., evapg., and distg. to collect the
fraction b0.6 185° gave 46% phenyl 6-quinolyl sulfide (IX). Refluxing 11 g. 6-mercaptoquinoline Na salt mixed with 0.5 g.
catalytic Cu with 14.1 g. PhBr to 100°, then slowly to 160° and keeping at 160° 1 hr., increasing the temp. to 165-70° and
keeping 2 hrs., dissolving in 100 cc. dil. H2SO4, heating to boiling, filtering, neutralizing with dil. NH3, extg. with Et2O,
treating the washed ext. with C, extg. with dil. HCl, treating with C, adding alkali, extg. with Et2O, evapg. and distg. gave
at 185°/0.6 mm. 18% IX. Oxidn. with CrO3 during 12 hrs. at 100° gave phenyl 6-quinolyl sulfone, m. 125-7° (C6H6-petr.
ether and EtOH). Heating slowly 11.6 g. p-aminodiphenyl sulfone with 8.5 g. As2O5, 18.4 g. glycerol, and 20 cc. H2SO4
to 150°, increasing the temp. during 5 hrs. to 160°, adding after cooling 3/4 of the amt. of H2SO4 necessary for
neutralization, filtering, boiling the filtrate with animal C, filtering, alkalinizing with NaOH, and washing the ppt. gave 35%
phenyl 6-quinolyl sulfone. 4-Nitro-4'-aminodiphenyl sulfide gave by the Skraup method 55% p-nitrophenyl 6-quinolyl
sulfide (X), m. 168.5-9.5° (washing with H2O and EtOH, crystd. from EtOH). X was also prepd. in 80% yield from 6-
mercaptoquinoline and p-C6H4Cl2. Reducing X with Raney Ni gave by pptg. with HCl gas from EtOH-Et2O p-
aminophenyl quinolyl sulfide-HCl (XI), m. 217-18°. Subjecting PhCH2Cl to the reaction described for II without heating,
keeping 1 hr., dilg. with H2O, and washing gave 90% benzyl 6-quinolyl sulfide (XII), m. 84-6° (ligroine and petr. ether).
The same method gave 58% p-nitrobenzyl 6-quinolyl sulfide (XIII), m. 127-8° (EtOH and AcOH), and 55% p-chlorobenzyl
6-quinolyl sulfide (XIV), m. 100-2° (EtOH). Adding to 10.3 g. p,p'-diaminodiphenyl sulfide, 17 g. As2O5, and 36.8 g.
glycerol slowly 40 g. H3SO4, heating 30 min. at 130-5°, increasing slowly to 145°, refluxing 5 hrs., cooling, dissolving in
H2O, adding 2 g. C, filtering, neutralizing with NH3, decanting, dissolving the mass in 35 cc. Me2CO and 65 cc. EtOH,
filtering, treating with C, adding 250 g. ground ice, filtering off the solid formed, washing with H2O, dissolving in HCl,
treating with C, and pptg. with NaOH gave 58% 6,6'-diquinolyl sulfide (XV), m. 116-17° (Me2CO). Oxidn. with CrO3 gave
at 100° in 18 hrs. 48% 6,6'-diquinolyl sulfone, m. 180-1° (EtOH). The compds. were tested for growth inhibiting power
with Candida albicans, Kloeckera brevis, Saccharomyces cerevisiae, Cryptococcus neoformans, Nocardia asteroides,
Trichophyton mentagrophytes, and Aspergillus niger. None of the sulfones was active. II, IV, V, IX, XII, XV, especially
XII, were of high activity as compared with 8-hydroxyquinoline and propyl p-hydroxybenzoate. I, VI, and VII were of low
activity.
~1 Citing
224. Monoglyceride diacetates as plasticizer and stabilizers for synthetic resins

By Ault, Waldo C.; Feuge, Reuben O.
CAPLUS
Plasticizer-stabilizer compns. having high stabilizer activity and high compatibility comprise epoxidized monoglyceride
diacetates of oils such as cottonseed, soybean, olive, corn, fish, and tall oil. Thus, 200 g. cottonseed oil was agitated
with 31.4 g. glycerol and 0.2 g. NaOH under an inert atm. for 5 hrs. at 200° and washed with H2O to free soap and
glycerol. Then 180 g. of the product was acetylated with Ac2O for 1 hr. at 110° to give a product with an Ac content of
about 10%. After washing and drying, 100 g. of the cottonseed oil monoglyceride diacetate (I no. 72.8) was treated with
190 cc. of a 20% soln. of peracetic acid in AcOH at 20-25° for 3 hrs., poured into H2O, washed with H2O, and extd. with
ether to give 99 g. of colorless oil (acid no. 4.5) contg. 3.57% epoxide O. The compn. was compatible with vinyl resins in
amts. ≤40% and showed no exudation on standing. Diacetylepoxystearin is also claimed.
~3 Citings
225. Monoesters useful as plasticizers

By Smith, Malcom K.
CAPLUS
Monoesters of hydroxy fatty acids useful as chem. intermediates and plasticizers for rubbers and resins were prepd. by
alcoholysis. A polyhydric alc. (4.5-9 moles) was treated with 1 mole triglyceryl ester, the latter derived from an acid
having 11-22 C atoms. The alc. had a max. of 1 primary OH and at least 1 secondary OH group (the latter undergoing
virtually no esterification) and included 1,2-propanediol (I) and 1,3-butanediol. The triglyceryl ester had up to 0.8% free
fatty acid, and was a liquid at reaction temp. Examples were castor oil (II), partially hydrogenated II (iodine no. at least
70), and a hydroxylated naturally occurring glyceride (iodine no. at least 40). The reaction was run under virtually anhyd.
conditions about 0.5-1.5 hrs. at 20-50°, using 0.01-1% alcoholysis catalyst (alkali metal hydroxide or alcoholate) based
on the wt. of the triglyceryl ester. The product was then neutralized with acid of dissocn. const. 10-2 to 10-11, washed free
of glycerine, alc., catalyst, and soap, and dried. If the reaction temp. was too high, sapon. occurred, causing loss of
catalyst and unwanted soap formation. In an example, a mixt. of II 300, I 225, and NaOH 0.9 parts by wt. was held 1 hr.
at 25-30° then kept overnight at ambient temp to give 2-hydroxypropyl ricinoleate (III), sapon. no. 158.3, n25 1.4701.
NaOH was dissolved in the I by warming. II had 0.22% free fatty acid. In other prepns., III had sapon. no. 158161.5 av.
159.4 (7 values), n25 1.4690-1.4711 av. 1.4699 (7 values), iodine no. 75.8-77.3 av. 76.25 (6 values), and hydroxyl no.
288.5 and 238.1. Similarly prepd. was 3-hydroxybutyl ricinoleate (IV), sapon. no. 149.1, and n25 1.4692. Acetylated
esters of III and IV, 2-acetoxypropyland 3-acetoxybutyl acetoxyricinoleate, resp., had sapon. no. 371.9 and 359.9, and
n25 D 1.4558 and 1.4579.
~3 Citings
226. Microbiological transformation of steroids. VII. 15β-Hydroxylation

By Herzog, Hershel L.; Gentles, Margaret Jevnik; Charney, William; Sutter, David; Townley, Edward; Yudis, Milton;
Kabasakalian, Peter; Hershberg, E. B.
DOI:10.1021/jo01087a600
Reichstein's compd. S (I) and progesterone (II) were converted to 4-pregnene-15β,17α,21-triol-3,20-dione (III) and 4-
pregnen-15β-ol-3,20-dione (IV), resp., by the action of Bacillus megaterium. Yeast ext. (10 g. Difco) and 10 g. Cerelose
made up to 1 l. and distributed equally among 10 300 ml. Erlenmeyer flasks, the sterilized media inoculated with B.
megaterium and incubated 16 hrs. at 28° with 220 r.p.m. shaking, 25 mg. I in 0.5 ml. 80% aq. alc. added to each flask
and incubation continued 24 hrs. to complete disappearance of I, the mixt. extd. with CHCl3 and the product crystd. from
Me2CO-C6H14 and Me2CO gave 0.128 g. III, m. 240-1° (decompn.), [α]25 D 103° (alc.), λ 242 mµ (ε 16,600, MeOH), λ
2.91, 5.83, 6.01, 6.18 µ (Nujol); III (130 mg.) in 4 ml. C5H5N kept 2.5 hrs. with 44 mg. Ac2O and the mixt. poured into
H2O, filtered and the product (100 mg., m. 226-31°) recrystd. (Me2CO-C6H14) gave 80 mg. 4-pregnene-15β,17α,21-triol-
3,20-dione 21-acetate (V), m. 244-6° (decompn.), [α]25 D 92° (alc.), λ 242 mµ (ε 17,700), λ 2.86, 2.96, 5.72, 5.77, 5.82,
6.06, 6.20, 8.10 µ. III (260 mg.) in 6 ml. C5H5N treated with 3 ml. Ac2O and the mixt. kept 16 hrs. at 20°, dild. with H2O
and the ppt. fractionated from Me2CO-C6H14 gave 20 mg. V and 180 mg. soft needles, m. 193-7°, chromatographed on
Florisil and recrystd. from Me2CO-C6H14 to give 4-pregnene-15β,17α,21-triol-3,20-dione 15,21-diacetate, m. 211-14°,
[α]25 D 56.8° (alc.), λ 239 mµ (ε 16,800), λ 3.15, 5.78, 5.80, 5.84, 6.06, 6.20, 8.20 µ. V (150 mg.) in 2 ml. C5H5N stirred
at 0° with 75 mg. CrO3 in 5 ml. C5H5N and the mixt. warmed slowly to room temp., stirred 16 hrs. and stirred 1 hr. with
0.5 g. Na2SO3 in 10 ml. H2O, poured into 200 ml. H2O and the ppt. (120 mg., m. 240-7°) recrystd. from Me2CO-C6H14
afforded 4-pregnene-17α,21-diol-3,15,20 trione 21-acetate, m. 258-60° (decompn.), [α]25 D 129° (Me2CO), λ 240 mµ (ε
17,300), λ 3.05, 5.75, 5.83, 6.10, 6.20, 8.15 µ. III (250 mg.) in 40 ml. AcOH dild. with 40 ml. H2O and stirred 16 hrs. at
20° with 5 g. NaBiO3, filtered and the filtrate and residue extd. with CH2Cl2, the H2O-washed ext. concd. and the residue
chromatographed over Florisil, the column eluted with Et2O and the fractions, m. 203-5°, recrystd. from CH2Cl2-C6H14
gave 60 mg. 4-androsten-15β-ol-3,17-dione (VI), m. 203-5°, λ 240 mµ (ε 16,900, MeOH), [α]25 D 120° (alc.), λ 2.99, 5.77,
6.01, 6.20 µ, not acetylated under conditions adequate for complete acetylation of most secondary hydroxyl groups. VI
(540 mg.) in 40 ml. AcOH treated 3 hrs. at 20° with 170 mg. CrO3 in 20 ml. 1:4 H2O-AcOH and dild. with H2O, the mixt.
extd. with CH2Cl2 and the product chromatographed over Florisil, eluted with 50% Et2O-C6H14 and the fraction (70 mg.,
m. 192-7°) recrystd. from Me2CO-C6H14 gave 4-androstene-3,15,17-trione (VII), m. 194-7°, [α]25 D 117.5° (MeOH), λ
241, 268 min., 275 mµ (ε 17,300, 7600, 7700, MeOH), λ 5.67, 5.78, 5.98, 6.22 µ (Nujol). The presence of a β-diketone
structure in VII suggested the possibility of ready titration with a strong base. VII (3.062 mg.) in 6.0 ml. 50% Me2SO in
H2O required 0.03954 ml. 0.2558N NaOH for neutralization yielding an equiv. wt. 303 and apparent pKa 6.17, indicating
the entry of OH into the 15β position. An inoculum of Saccharomyces cerevisiae (300 ml.) added to a sterile medium
contg. 600 g. Cerelose and 100 g. yeast ext. made up to 1 l. with tap H2O buffered at pH 6.8 (phosphate buffer) and the
mixt. incubated at 28° 42 hrs. with aeration (0.5 vol. air/vol. medium/min.), 0.5 g. VI in 10 ml. MeOH added and the
incubation continued 3 days with increased aeration (1.5 vol. air/vol. medium/min.), the mixt. extd. with CHCl3 and the
product crystd. from CH2Cl2-C6H14 gave 0.2 g. 4-androstene-15β,17β-diol-3-one (VIII), m. 220-2° [α]25 D 57° (alc.), λ 242
mµ (ε 15,000, MeOH), λ 2.94, 3.12, 6.05, 6.21 µ. The phys. consts. of VI and VIII were notably different from those
reported for 4androsten-16α-ol-3,17-dione and 4-androstene-16α,17β-diol-3-one and, consequently, 16α was rejected as
a likely position for the entering OH group. It was supposed that degradation of III with KIO4 to the corresponding 17β-
carboxylic acid should lead to lactone formation involving the 15β-OH group. III (40 mg.) in 4 ml. MeOH treated with 14.5
g. KIO4 (1.18 g./200 ml. H2O) and the mixt. kept overnight in the dark, made acid with a few drops of 10% H2SO4 and
after 30 min. at 20° adjusted to pH 5.0-6.0 with NaOH in MeOH, treated with 1 drop glycerol and concd. in an air stream
gave 26 mg. 15β,17α-dihydroxy-3-oxo-4-etienic acid, m. 265-70° (decompn.), λ 241 mµ (ε 16,400), λ 2.89, 3.01, 3.14,
5.75, 5.89, 6.14, 6.22 µ, apparent pH 4.4 in Me2SO-H2O (apparent pH 7.3); Me ester, m. 199-201° (MeOH-H2O), [α]25 D
50° (dioxane), λ 242 mµ (ε 15,500), λ 2.96, 5.79, 6.01, 6.21,8.33 µ (Nujol). The steric hindrance which inhibited
acetylation could be a factor preventing lactonization. Hydroxylation of II with B. megaterium gave a low yield of IV and
at least 9 other ultraviolet absorbing substances as indicated by paper chromatography. On the contrary, 1-
dehydrocortisol and 1-dehydrocortisone were reduced in low yields to cortisol and cortisone, resp., without formation of
15β-hydroxylated derivs. Microbiol. redn. of the 1,2 double bond in steroids has not been previously noted.
~1 Citing
227. Influence of trace impurities on the quality of distilled glycerol in storage. Determination of the aldehyde
content
By Grynberg, H.; Szeczepanska, H.
From Oleagineux (1959), 14, 585-9. Language: Unavailable, Database: CAPLUS
Aldehydes in glycerol were quant. detd. by pptn. as 2,4-dinitrophenylhydrazones. The pptd. mixt. was chromatographed
on acetylated paper, and the exts. of the spots were checked colorimetrically for their phenylhydrazone content. With
this method an aldehyde content in the range from 0.3 to 30 µg. could be detd.
~0 Citings
228. Incorporation of sodium hexanoate-1-C14 and sodium hydrogen carbonate-C14 into milk constituents by
the perfused cow's udder
By Lauryssens, Monique; Verbeke, R.; Peeters, G.; Donuck, Agnes
From Biochemical Journal (1959), 73, 71-5. Language: Unavailable, Database: CAPLUS, DOI:10.1042/bj0730071
Perfusions of 2 halves of lactating cow udders were performed for 2 hrs. with blood contg. bicarbonate-C14 and
hexanoate-1-C14. Both halves received inactive acetate added continuously throughout the expts., and 150 and 290 ml.
of milk, resp., were collected after perfusion. A slight incorporation of C14O2 occurred in milk casein, largely in aspartic
acid and glutamic acid. Citric acid isolated from the milk of the same half-udder showed a higher activity. In the
hexanoate expt. the specific activity of CO2 was low at the beginning but increased gradually; approx. 4% of the C14 was
recovered as C14O2. The specific activities of the milk constituents of the hexanoate expt. decreased in the following
order: citric acid, casein, lower fatty acids, higher fatty acids, and lactose. Cholesterol, glycerol, and phospholipides did
not show any detectable activity in milk. Fatty-acid fractions isolated from udder tissue were approx. 40 times as active
as the corresponding milk fatty acids. The specific activity of the lower fatty acids from udder and milk increased with
increasing chain length to reach a max. at C8 and then fell progressively with further increase of chain length. In the
hexanoate expt. 14% of the added C14 was recovered in fat at the end of the expt. There was no evidence of direct
esterification of hexanoate-1-C14. Of the activity of milk casein obtained from the hexanoate expt., 97% was the result of
glutamic acid and aspartic acid, the activity of the former being 3 times that of the latter. These results are consistent
with the assumption that hexanoate-1-C14 is broken down to C2 components with high acetylating capacity. These
components are utilized for the synthesis of fatty acids and are metabolized by way of the Krebs cycle, which is
demonstrated by the isolation of citric acid, succinic acid, and fumaric acid with high specific activity. Hexanoate did not
behave in a glycogenic manner in the perfused udder. The carbonate pool is involved only to a negligible extent in the
incorporation of C14 from hexanoate into milk constituents by the perfused-udder prepn. The specific activities of the
different fractions may be a reflection of the secretory processes of the udder cells. The fat formed in the cells is
secreted in the alveoli at a later time than in the other milk constituents.
~0 Citings
229. Changes in the chemical, physical, and dyeing characteristics of viscose fibers after treatment with water
and steam at elevated temperatures. II
By Rexroth, Erhard
From Textil-Praxis (1959), 14, 388-96. Language: Unavailable, Database: CAPLUS
cf. C.A. 53, 13598i. Initially, the viscose fibers were cleaned, extd. with EtOH and ether, and then conditioned for 3 days
at 65% relative humidity. Swelling values were detd. by immersion of the samples of about 0.3 g. in a 0.1% soln. of a
wetting agent for 10 min. at 25°. The fibers were then pressed and centrifuged for 1 min. at a centrifugal acceleration of
about 486,000 cm. sec.-2 Weighing of samples and subsequent drying for 1 hr. at 105° was followed by cooling in a
desiccator for 15 min. and reweighing. Swelling values under conditions used for vat dyeing, i.e., temps. of 25-60° and in
the presence of 0.5-1% NaOH, were detd. also. The max. swelling of 91.0% was obtained with 1% NaOH at 25° for an
untreated fiber; the min. value of 57.5% was obtained in water at 60° for a fiber treated with steam at 3 atm. The
smallest difference in swelling of treated and untreated fibers was obtained at 60° in the 1% NaOH bath, which agrees
with the observation that dye bath penetration of treated and untreated fibers approach each other under these
conditions. Steaming at 3 atm. for 1 hr. at 133° or pressure-cooking for 1 hr. at 140° did not affect the phys. strength
characteristics of the fiber, although a slight drop in the degree of polymerization of 0 to 5% took place. The swelling
value in water could be reduced appreciably with dil. HCl, H2SO4, HCOOH, and solutions of NH4Cl and (NH4)2SO4. This,
however, did not reduce the affinity to vat dyes. Tests for carboxyl groups in the treated fibers were neg., disproving the
possibility of fiber oxidn. Steamed fibers always show slight yellowing, which stems from the presence of a degradation
product. This may be removed by heating with water at temps. above 100° or by heating with glycerol at 150-200°.
Thereupon, dye receptivity, leveling, and swelling value increase somewhat without reaching the original value. The
irreversible reduction in the swelling value could not be explained by an increase in crystallinity, since the ratio of cryst. to
amorphous regions in the fiber remained the same after treatment with water or steam. However, x-ray diffraction
revealed a structural change, with cellulose II gradually changing into cellulose IV, as evidenced by the disappearance of
the A 3 reflex and the formation of a reflex at 2 θ = 15°54'. Treatment was responsible for the formation of a shrunken
annular layer in the fiber. After this outer zone had been converted to acetyl cellulose by controlled acetylation, it could
be removed from a 20-g. sample with a mixt. of dry benzene 960, freshly distd. Ac2O 240, and concd. H2SO4 2 cc. With
an acetylation time of 20 hrs., the swelling values of treated and untrated fibers were the same after removal of the
acetylated material. The loss in wt. was 10% in both cases.
~0 Citings
230. Aspects of stereochemistry. II. Intramolecular hydrogen bonding in monohydroxy derivatives of

tetrahydrofuran, tetrahydropyran, and 1,3-dioxane
By Barker, S. A.; Brimacombe, J. S.; Foster, A. B.; Whiffen, D. H.; Zweifel, G.
From Tetrahedron (1959), 7, 10-18. Language: Unavailable, Database: CAPLUS, DOI:10.1016/0040-4020(59)80046-6
cf. C.A. 53, 12219c. The infrared absorption frequencies of monohydroxy derivs. of tetrahydrofuran, tetrahydropyran,
and 1,3-dioxane were detd. in 0.005M (or lower) CHCl3 solns. (alc., absorption frequency free OH (in cm.-1) and relative
extinction coeff. (ε), and absorption frequency bonded OH (ε) given): 2-tetrahydropyranol, 3620 (40), -; 3-
tetrahydropyranol (I), 3620 (40), 3604 (50); 4-tetrahydropyranol, 3622 (40), -; 2-(hydroxymethyl)tetrahydropyran, -, 3597
(50); 2-tetrahydrofuranol, 3619 (40), -; 3-tetrahydrofuranol, 3628 (48), -; 2-(hydroxymethyl)tetrahydrofuran, -, 3600 (47);
1,3-O-methyleneglyceritol (II), 3635 (21), 3594 (100); 1,3-O-ethylideneglyceritol (II), -, 3593 (50); 1,3-O-
propylideneglyceritol, -, 3590 (100); 1,3-O-isobutylideneglyceritol, -, 3589 (55); 1,3-O-benzylideneglyceritol, -, 3593 (78);
trans-2-phenyl-1,3-dioxan-5-ol, 3633 (55), 3593 (70). The extent of intramol. H bonding between OH groups and ring O,
as detd. by infrared absorption data on the OH stretching region, provides direct exptl. evidence for the stabilities of
different conformations of certain of the alcs. BzO2H (15 g.) in 200 ml. aq. satd. Et2O at 0° kept 24 hrs. with 9 g. 2,3-
dihydropyran (IV) and the mixt. extd. with H2O, the ext. washed with Et2O and evapd. at 40°/12-15 mm. yielded crude
2,3-dihydroxytetrahydropyran, acetylated 48 hrs. at room temp. with 15 ml. Ac2O in 30 ml. dry C5H5N and the mixt.
poured into H2O, extd. with CHCl3, and the washed and dried ext. evapd. to give 2,3-diacetoxytetrahydropyran, b0.01 70-
2°, n20 D 1.4458. The diacetate (5 g.) in 50 ml. Et2O (satd. with HCl at 0°) kept 48 hrs. at 0° and evapd. in vacuo, the
residue repeatedly distd. from C6H6 and the HCl-free sirup refluxed 4 hrs. in Et2O over 7.5 g. LiAlH4 the excess reagent
destroyed with H2O and ppt. taken up in aq. Rochelle salt soln., the soln. exhaustively extd. with Et2O, and the residue
on evapn. distd. yielded I, b12-15 92-5°, n21 D 1.4571, nonreducing towards Fehling soln., and giving a sirupy p-
MeC6H4SO2 deriv., C12H16O4S. Formation of I via the redn. of 2,3-epoxytetrahydropyran was examd. but proved
unsuitable since, under the exptl. conditions, any epoxide, if formed, underwent further reaction. BzO2H (10 g.) in 200
ml. dry CHCl3 at -5° treated 10 min. with 6 g. IV and the soln. extd. 3 times with cold 2N NaOH and with H2O, the dried
CHCl3 soln. evapd., and the residue recrystd. (Et2O-ligroine, b. 60-80°) gave trans-2-benzoyloxy-3-
hydroxytetrahydropyran (V), m. 85-7°, v 1703, 1720, 3460 cm.-1 (Nujol). V (3.5 g.) in 20 ml. dry C5H5N at 0° kept 30 hrs.
with 4 g. BzCl in 20 ml. C5H5N and the mixt. dild. with CHCl3, the soln. washed (dil. HCl, H2O, 10% aq. CdCl2, dil. aq.
NaHCO3), and the dried soln. (Na2SO4) evapd. gave 5 g. trans-2,3-dibenzoyloxytetrahydropyran (VI), m. 70-5° (MeOH),
v 1721, 1736 cm.-1 (Nujol). Treatment of VI with HCl-Et2O followed by redn. with LiAlH4 gave an inseparable mixt. of
PhCH2OH and, presumably, I. The mechanism of the reaction of BzO2H with glycols was discussed. CHCl3 (20 ml.)
contg. 3 g. 2-O-benzoyl-1,3-O-methyleneglyceritol treated with 5 ml. dry MeOH contg. a trace of Na and kept 24 hrs. at
room temp. the soln. neutralized with solid CO2 and evapd., the residue taken up in H2O and the soln. washed with
ligroine, extd. exhaustively with Et2O, and the ext. evapd. gave II, b11 80-5°, n20 D 1.4540, also prepd. by sapon. of the
benzoate with aq. alkali according to Hibbert and Carter (C.A. 23, 98). AcH (15 g.) passed into 34 g. glyceritol and 1.0
ml. concd. H2SO4 and the mixt. neutralized with solid K2CO3, the mixt. washed with ligroine and taken up in Et2O, the
soln. washed (H2O), and evapd. yielded a residue contg. 29 g. O-ethylideneglyceritols, b0.05 45-8°. The mixed glyceritols
(25 g.) in 100 ml. dry C5H5N treated 10 hrs. at 0° with 26 g. BzCl yielded 5-benzoyloxy-2-methyl-1,3-dioxane (VII), m.
86°. Debenzoylation with NaOMe in MeOH yielded authentic III, b0.05 40-5°, n21 D 1.5152.
~9 Citings
231. Actinomycetes dyes. VI. Pyrromycinones

By Brockmann, Hans; Lenk, Werner
cf. C.A. 50, 9359f. Three cryst. dyes were isolated from the Streptomyces strain DOA 1205 and designated η (I), ζ (II),
and ε-pyrromycinone (III). I was 1,4,6-trihydroxy-8-carbomethoxy-9-ethylnaphthacenequinone, II was 1,4,6,7-
tetrahydroxy-8-carbomethoxy-9-ethyl-7,8,9,10-tetrahydronaphthacenequinone, and III was the 9-OH deriv. of II. II and III
could be converted by dehydrogenation and dehydration, resp., to I. The pyrromycinones (IV) were related to the
rhodomycinones to which they could be related structurally via η-isopyrromycinone (V), obtainable from I. Nutrient (800
l.) (2 vol.-% glycerol, 0.25% H2NCH2CO2H, 0.10% NaCl, 0.10% K2HPO4, 0.01% FeSO4.7H2O, 0.01% MgSO4.7H2O, and
0.01% CaCO3) sterilized at 2 atm. gage in 800 flasks, each flask inoculated with the mycelia from a Ca malate-agar
culture, and incubated 4 weeks at 30°, filtered, concd. to 500 l., and extd. with BuOH, the BuOH ext. evapd., the brown
tacky residue dissolved in 1 l. CHCl3, washed with 1 l. H2O, and evapd. left crude product B. The moist mycelia stirred 1
hr. with 4 l. Me2CO, the red ext. decanted, the extn. repeated 3-4 times daily with 3 l. Me2CO until the ext. was only
slightly colored, and the combined exts. evapd. left brown, tacky, crude product M; the 1st Me2CO ext. contg. the H2O
from the mycelia evapd. separately gave addnl. crude product M. The mycelia then treated repeatedly with Me2CO
contg. 0.5% HCl, neutralized with concd. NH4OH, centrifuged to remove the NH4Cl, and evapd. gave addnl. product M.
The combined products B and M extd. repeatedly with petr. ether (b. 40°) left 157 g. crude dye P; the combined red
petroleum exts. extd. 1 week in a Soxhlet app. with Et2O left crude IV mixt. (117 g.), brown powder; the Et2O ext. evapd.
gave 40 g. IV mixt. The IV mixt. in 500 cc. C6H6 chromatographed on 4 silica gel columns gave 3 zones in the order III
(top), II, I. Zone I eluted with C6H6 and rechromatographed on silica gel gave 3.7 g. I, dark red needles, m. 236-7°. I
(200 mg.) in 5 cc. C5H5N and 10 cc. Ac2O heated 1 hr. at 80°, poured into H2O, and extd. with CHCl3, and the ext.
chromatographed on silica gel gave 5 mg. partially acetylated I, red-yellow needles, m. 207-8° (MeOH), and 235 mg.
triacetate (VI) of I, lemon-yellow needles, m. 205-6° (MeOH). I (100 mg.) and 60 cc. 2N KOH-MeOH refluxed 3 hrs.,
cooled, acidified with 25 cc. 25% H2SO4, and filtered, the residue dried and dissolved in 250 cc. CHCl3, the soln. filtered
through silica gel, and the eluate of the main zone evapd. in vacuo yielded η-pyrromycinonic acid, red needles, m. 263°
(decompn.) (glacial AcOH). VI (100 mg.), 50 mg. NaOAc, 300 mg. Zn dust, and 40 cc. Ac2O refluxed 2 min., poured into
H2O, and extd. with 50 cc. C6H6, the ext. chromatographed on silica gel, and the eluate of the lowest zone evapd. gave a
red-yellow amorphous residue (VII) which in C6H6 was greenish yellow, λ 482, 452, 424, and 400 mµ. I (200 mg.) in 40
cc. 2N KOH, refluxed 3 hrs., cooled, acidified with 30 cc. 25% H2SO4, and extd. with CHCl3, the ext. reëxtd. with aq.
NaHCO3, the aq. ext. acidified with 10 cc. 25% H2SO4, the ppt. dissolved in 50 cc. Et2O, the soln. stirred with 30 cc. satd.
aq. Ca(OH)2, the Et2O evapd., the salt filtered off, dried over P2O5, and heated in vacuo at 230-50° 2 hrs., the violet
residue acidified with 1 cc. 25% H2SO4 and extd. with C6H6, the ext. combined with the C6H6 soln. of the sublimate and
evapd., and the residue chromatographed from 1:1 C6H6-ligroine on silica gel gave decarbomethoxy deriv. (VIII) of I, dark
red needles, m. 229-30°. VIII (10 mg.) in 5 cc. Ac2O treated with a few drops 60% HClO4, poured into 50 cc. H2O, and
extd. with 20 cc. CHCl3, the ext. chromatographed on silica gel, and the upper zone eluted and evapd. gave the
triacetate (IX) of VIII, yellow needles, m. 217-19° (decompn.). I (68 mg.) in 40 cc. concd. H2SO4 treated in portions of 10
cc. with a small amt. of freshly prepd. MnO2, dild. after 1-2 min. with 5 vols. H2O, and extd. with two 50-cc. portions C6H6,
and the ext. washed with aq. NaHSO3, dried, and chromatographed on silica gel yielded 40 mg. V, ruby-red needles, m.
229-30° (ligroine-C6H6). The crude II from the original chromatogram eluted with C6H6, concd. to 1/2 the vol., and then
rechromatographed yielded 15 g. pure II, fire-red needles, m. 216° (C6H6), [α]20 Cd 74 ± 6° (c 1.0, CHCl3). II (185 mg.)
treated with 7 cc. Ac2O contg. 1 drop 60% HClO4, poured into 50 cc. H2O, and filtered, the residue dried and dissolved in
20 cc. CHCl3, the soln. chromatographed on silica gel, and the eluate of the lowest zone evapd. gave 16 mg. partially
acetylated II, m. 169-70° (decompn.) (MeOH); the upper zone yielded the tetraacetate (X) of II, light yellow needles, m.
195-6° (MeOH), [α]22 D 15 ± 4° (c 1.0, CHCl3). X (135 mg.), 100 mg. Zn dust, and 5 cc. Ac2O refluxed 0.5 hr., poured
into 50 cc. H2O, and extd. with 25 cc. C6H6, and the ext. chromatographed on silica gel gave a colorless residue (XI)
which fluoresced strongly blue in org. solvents. II (37 mg.) and 25 cc. CrO3-H2SO4 (1 part concd. H2SO4 and 5 parts 5N
H2CrO4) heated in a N stream at 130° and steam distd., and the distillate (about 30 cc.) neutralized with 0.02N NaOH
and evapd. in vacuo left NaOAc. II (600 mg.) in 15 cc. C5H5N treated with 0.1/N KMnO4 in C5H5N in small portions until
the color persisted, dild. with 5 cc. 2N NaOH and a few drops H2O2, filtered, and evapd. in vacuo to remove the C5H5N,
the residual aq. soln. adjusted with Dowex 50 (H form) to pH 5, and steam distd., and the distillate (about 40 cc.)
neutralized with NaOH and evapd. gave NaOAc and EtCO2Na. II (180 mg.) and 40 cc. 2N KOH in 1:1 MeOH-H2O
refluxed 0.5 hr., cooled, acidified with 20 cc. 25% H2SO4, and filtered, and the residue dried and chromatographed from
200 cc. CHCl3 on silica gel yielded ζ-pyrromycinonic acid, red needles, m. 190° (decompn.) (sealed capillary), which
contained 2.47% CHCl3. II (106 mg.), 240 mg. active MnO2, and 50 cc. concd. H2SO4 oxidized and worked up in the
usual manner and the C6H6 soln. of the product chromatographed on silica gel gave 15 mg. 9,10(or 7,8)-dihydro deriv. of
V, ruby-red, m. 197-8°. II (170 mg.) refluxed 0.5 hr. with 30 cc. 2N KOH and acidified with 20 cc. 25% H2SO4, the ppt.
suspended in 30 cc. Et2O and stirred with 20 cc. satd. aq. Ca(OH)2, and the resulting Ca salt dried over P2O5 and heated
2 hrs. in vacuo at 280° gave a red sublimate of VIII; the violet sublimation residue acidified with 1 cc. 25% H2SO4 and
extd. with C6H6, and the ext. worked up gave 25 mg. VIII, red needles, m. 229-30°. II (20 mg.) heated in vacuo at 200°,
and the glassy sublimate chromatographed from 50 cc. C6H6 on silica gel yielded the dihydro deriv. (XII) of VIII, light red
crystals, m. 169-71° (ligroine, b. 110°). II (130 mg.) in 10 cc. 48% HBr refluxed 2 hrs. with 25 cc. glacial AcOH, poured
into 50 cc. H2O, and extd. with two 50-cc. portions C6H6, and the ext. chromatographed on silica gel yielded XII, ruby-red
prisms and light red crystals, m. 177-8° (sublimed in vacuo at 180-200°). XII (50 mg.) and 37 mg. Pd-C heated 1.5 hrs.
at 220° and the sublimate chromatographed from 50 cc. 1:1 C6H6-ligroine on silica gel yielded 23 mg. VIII, dark red
needles, m. 229-30°. II (100 mg.), 100 mg. Pd black, and 150 mg. Pd-C heated 1 hr. at 280° and the sublimate
chromatographed from C6H6 on silica gel yielded 28 mg. I, m. 237°. II (63 mg.) heated 0.5 hr. at 220-30°, dissolved in 40
cc. C6H6, and chromatographed from C6H6 on silica gel yielded the dihydro deriv. (XIII) of I, brown-red needles, m. 206-
7°. XIII (7 mg.) and 10 mg. Pd-C heated in vacuo at 220° gave 2 mg. I. II (210 mg.) and 500 mg. P2O5 heated 5 min.
with stirring at 150° and extd. with 100 cc. C6H6, and the ext. chromatographed on silica gel yielded C22H18O7, fire-red
needles, m. 158-9° (glacial AcOH or ligroine); a 14-mg. portion and 10 mg. Pd-C heated in vacuo at 220° yielded 4 mg. I.
The crude III from the original chromatogram rechromatographed on silica gel gave pure III, fire-red needles, m. 213-14°
(C6H6) (sealed capillary), [α]20 Cd 143 ± 7° (c 1.0, CHCl3). III (106 mg.), 1 cc. Ac2O, and 0.5 cc. C5H5N kept overnight,
poured into H2O, and extd. with CHCL3, and the ext. chromatographed on silica gel yielded 61% tetraacetate of III, light
yellow needles, m. 219-21° (MeOH) (decompn.), [α]18 D -10.3 ± 2° (c 1.0, CHCL3). III (36 mg.) oxidized with 18 cc. CrO3-
H2SO4 and the distillate (about 20 cc.) neutralized with 3.2 cc. 0.02N NaOH and evapd. left a mixt. of about equal parts
NaOAc and EtCO2Na. III (20 mg.) heated in vacuo at 180-220° and the sublimate (9 mg.) chromatographed from C6H6
on silica gel yielded cryst. I. III (100 mg.) dissolved in 30 cc. glacial AcOH and 5 cc. HBr (d. 1.49) and cooled deposited
77% I, red needles. The ultraviolet absorption spectra were given of I, VII, XI, 6,11-diacetoxynaphthacenequinone, 1,4,6-
(XIV) and 1,6,11-trihydroxynaphthacenequinone, of I in cyclohexane and in concd. H2SO4, and of II, 1,4,5-
trihydroxyanthraquinone (XV), VI, IX, X, XI, and the triacetates of XIV and XV in MeOH.
~3 Citings
232. Triiodobenzoic acid compounds

By Wiegart, Philip E.; Rands, Robert D., Jr.
CAPLUS
Na metal (2.3 g.) was dissolved in 200 mL. MeOH, then 19.7 g. Me 3-hydroxy-5-nitrobenzoate (I) was added, and 11.1 g.
glycerol α-monochlorohydrin, and the mixt. refluxed 24 h. to give Me 3-(2,3-dihydroxypropoxy)-5-nitrobenzoate (II).
Na2CO3 (30 g.) in 150 mL. H2O was added, the II hydrolyzed, and the MeOH distd. to leave the acid (III), m. 115-20°,
and NaCl. III was hydrogenated to the amino acid and then converted with ICl to the 2,4,6-triiodo acid, m. 197-9°. The
amino group was acetylated by Ac2O and H2SO4. The Na then the N-methylglucamine salts of the 3-acetamido-5-(2,3-
dihydroxypropoxy)-2,4,6-triiodobenzoic acid (IV) were made. The latter salt had L.D.50 > 14.7 g./kg. In a similar way I
was converted to IV amide, m. 251.5-2.5° (decompn.). These acid derivs. were used in the prepn. of x-ray contrast
material.
~2 Citings
233. Synthesis of a β-batyl (glycerol 2-octadecyl ether) analog of cephalin, and melting point data for batyl,
chimyl, β-batyl, and β-chimyl alcohols and their derivatives
By Bevan, T. H.; Malkin, T.
DOI:10.1039/JR9600000350
A stearoyl-β-batyl analog (I) of cephalin (II) was prepd. by the method previously described (C.A. 53, 3048f) for the
isomeric batyl analog (III). I and III had the same m.p., but were readily distinguished by their short x-ray spacings and
by the ease with which III was dephosphorylated by AcOH-Ac2O mixt. M.p. data were given for batyl (IV), chimyl (V), β-
batyl (VI) and β-chimyl alcs. (VII), and their di-Ac and ditrityl derivs. and diphenylcarbamates. Octadecyl iodide and K
O,O-benzylideneglycerol in refluxing C6H6 gave 10% VI, m. 71°. This was improved to 30% by the use of xylene as a
solvent. The benzylideneglycerol, m. 84°, instead of the mixt. of geometrical isomers was used. 1,3-O-
Benzylideneglycerol (18 g.) added in portions to 3.9 g. finely powd. K under 300 ml. xylene, the reaction completed by
refluxing, 60 g. octadecyl iodide added, refluxing continued 20 hrs., cooled, the KI removed, the filtrate evapd., and the
residue distd. to remove starting materials gave 17 g. residue, which crystd. gave 13 g. product, m. 57-8°. The
benzylidene group was removed by hydrolysis or hydrogenolysis. The latter was the superior method. The benzylidene
deriv. (11 g.) refluxed 70 min. in 150 ml. alc. and 50 ml. H2O contg. 11 ml. concd. HCl, cooled, dild. with H2O, and the
solid collected gave 7 g. VI. The benzylidene compd. (1.08 g.) hydrogenated in 40 ml. EtOAc at atm. pressure in the
presence of 0.3 g. Pt black, after hydrogenation the soln. warmed, the catalyst removed, and the soln. evapd. gave a
quant. yield of VI. Similarly, hexadecyl iodide gave 30% intermediate benzylidene deriv., m. 38-9°. Hydrolysis or
hydrogenolysis gave VII, m. 63° (Me2CO). Stearoyl chloride (3.03 g.) added dropwise to 3.44 g. VI in 50 ml. CHCl3
contg. 3 ml. C5H5N, the mixt. stirred 20 hrs. the solvent removed, the residue triturated with H2O, filtered, and dried gave
5.3 g. β-batyl monostearate (VIII), m. 57-9°(alc. and Me2CO). VIII (4.72 g.) added portionwise to 2 g. p-MeC6H4SO2Cl in
14 ml. C5H5N, kept 2 hrs. at 40°, poured into H2O, and collected gave 4.6 g. stearoyl-β-batyl p-toluenesulfonate (IX), m.
70° (alc. and ligroine). IX (3.5 g.) refluxed 24 hrs. in the dark in 50 ml. Me2CO contg. 2.25 g. NaI, the 0.83 g. Na p-
toluenesulfonate removed, and the filtrate cooled gave 3.9 g. stearoyl-β-batyl iodide (X), m. 60° (Me2CO). X also existed
in a form m. 41-2°. X (2.6 g.) added to 2 g. Ag 2-(benzyloxycarbonylamino)ethyl phenyl phosphate in 60 ml. refluxing
xylene in the dark, stirred 15 min., the pptd. AgI removed, the solvent removed in vacuo, the residue dissolved in Et2O,
and evapd. gave 3 g. solid. This solid in AcOH-CHCl3 hydrogenated over Pd black and PtO2 and evapd. gave 1.5 g. β-
batyl cephalin (XI), m. 198° (alc.). On evapn. of the other ext. there remained 0.7 g. VIII. The identity of VIII was
confirmed by refluxing 0.5 g. X with 0.5 g. AgNO3 in 20 ml. alc. contg. 1 ml. H2O, removing the pptd. Ag salt, and evapg.
the solvent to give 0.3 g. VIII. III gave 86% batyl 1-acetate 2-stearate by the action of AcOH-Ac2O, m. 41-2° (alc.) and
47° (hexane). I treated in the same manner gave product, m. 70°, which was difficult to purify. Batyl 1-stearate, m. 71°,
was prepd. by monoacylation of IV in CHCl3-C5H5N. This stearate (0.3 g.) heated 8 hrs. in AcOH-Ac2O 8 hrs. gave 0.3
g. batyl 1-acetate 2-stearate, dimorphous, m. 49° (hexane). β-Batyl 1-acetate 3-stearate was prepd. for comparison by
the acetylation of β-batyl monostearate, dimorphic, m. 42-3°(alc.) and 49-50° (hexane). IV (0.5 g.) heated 1 hr. with 5 ml.
Ac2O, the cold soln. poured into H2O, and 0.5 g. product collected gave IV diacetate, transparent wax, m. 35°, slowly
changing to opaque form, m. 43°. The remaining diacetates were prepd. similarly, except that VII diacetate was more
conveniently extd. by Et2O. All existed in at least 2 forms. VI diacetate m. 29° and 34°; V diacetate m. 24° (from MeOH
at 0°) and 33° (opaque form); VII diacetate m. 18° and 26°. The ditrityl derivs. were obtained from Ph3CBr and the alc. in
C5H5N. The following were obtained: ditritylbatyl alc., m. 71° (Me2CO) (82% yield); ditrityl-β-batyl alc., 81° (87%);
ditritylchimyl alc., m. 62° (70%); ditrityl-β-chimyl alc., m. 69° (75%). The diphenylcarbamates were prepd. by heating the
alcs. in C6H6 with PhNCO 1 hr. under anhyd. conditions, reducing the soln. in vol., and pptg. the carbamates by the
addn. of ligroine. Final crystn. was from a mixt. of ligroine-C6H6. The following were obtained: batyl diphenylcarbamate,
m. 97° (80%); β-batyl diphenylcarbamate, m. 93° (85%); chimyl diphenylcarbamate, m. 95° (80%); β-chimyl
diphenylcarbamate, m. 88° (90%). The short x-ray spacings of cephalins and analogs were given in a table. It was
noted that only the β-isomers crystd. in spherulite formations.
~0 Citings
234. Substitution of 5-(n-pentadecyl)resorcinol

By Parkh, Sindhu; Sethna, Suresh
From Journal of the Indian Chemical Society (1960), 37, 159-62. Language: Unavailable, Database: CAPLUS
5-(n-Pentadecyl)-resorcinol condensed with Et acetoacetate and malic acid to yield 5-hydroxycoumarin derivs. On
carboxylation, Gattermann formylation, and Friedel-Crafts acetylation, substitution took place in the 2-position. A mixt. of
2 g. 5-(n-pentadecyl)resorcinol, 2 g. Et acetoacetate and 8 cc. concd. H2SO4 was kept overnight and poured onto ice to
give 1.3 g. 5-hydroxy-4-methyl-7-(n-pentadecyl)coumarin, m. 142-3 (EtOH); acetyl deriv. m. 89-91°; Me ether m. 85-6°.
2,6-Dihydroxy-4-(n-pentadecyl)benzoic acid was prepd. by mixing to 10 g. 5-(n-pentadecyl)resorcinol with 20 g. KHCO3
and 20 g. anhyd. glycerin, heating the mixt. 5 hrs. on an oil bath in a current of CO2 at 115-20°, cooling, adding H2O, and
acidifying with HCl to give 6 g. product, m. 136-8°, blue coloration with alc. FeCl3. Me 2,6-dimethoxy-4-(n-
pentadecyl)benzoate, needles, m. 42-3°, hydrolyzed by refluxing 10% alc. KOH gave 2,6-dimethoxy-4-(n-
pentadecyl)benzoic acid, m. 88-9°. 7-Hydroxy-5-(n-pentadecyl)-4-methylcoumarin-8-carboxylic acid, m. 180°, was
decarboxylated to yield 7-hydroxy-5-(n-pentadecyl)-4-methylcoumarin, m. 127-8°. 2,6-Dihydroxy-4-(n-
pentadecyl)benzaldehyde, needles, m. 95-6°; di-Me ether m. 88-9°. 5-Hydroxy-7-(n-pentadecyl)-3-acetylcoumarin,
yellowish needles, m. 150-2°, showed no fluorescence with concd. H2SO4 and no color with FeCl3. 5-Hydroxy-7-(n-
pentadecyl)coumarin, needles, m. 125-7°; it developed a yellow color with alkali. 2,6-Dihydroxy-4-(n-
pentadecyl)acetophenone m. 74-6°, red coloration with alc. KOH. 2,4-Diacetyl-5-(n-pentadecyl)resorcinol m. 60-2°, red
coloration with alc. FeCl3.
~0 Citings
235. Steroids. XIV. Transformation of steroids by Pseudomonas. 1

By Uchibayashi, Masao
From Chem. & Pharm. Bull. (Tokyo) (1960), 8, 112-16. Language: Unavailable, Database: CAPLUS
cf. CA 53, 11435i. Pseudomonas sp. 109 (I) converted 17α,21-dihydroxy-4-pregnene-3,20-dione (II) into 17α,20β,21-
trihydroxy-1,4-pregnadien-3-one (III) and 11β,17α,21-trihydroxy-4-pregnene-3,20-dione (IV), and the structure of III was
verified. Incubation of 10 g. II (30°, 17 hrs.) with a 24-hr. growth culture of I in a medium contg. glycerol, urea, MgSO4,
KH2PO4, and FeSO4, and extn. of the culture filtrate with AcOEt yielded 3.4 g. powdery residue from the evapd. ext. This
(3.4 g.) was acetylated with Ac2O in C5H5N to yield 0.75 g. 17α-hydroxy-20β,21-diacetoxy-1,4-pregnadien-3-one (V), m.
178-9°, [α]20 D 100° (c 1, CHCl3). The evapd. mother liquor from V left a residue, which was chromatographed in C6H6
over Florisil to yield 0.33 g. V, and 60 mg. IV 21-acetate (VI), m. 214-16°, identical with an authentic sample by mixed
m.p. and infrared absorption. Hydrolysis of 0.65 g. V with KHCO3 yielded 0.22 g. III, m. 194-5°, [α]20 D 33° (c 1, CHCl3),
evidently the main product of the microbiol. conversion of II by I. Subjected to paper chromatography, III showed a spot
characteristic of a 1,4-dien-3-one compd. which by its fluorescence in ultraviolet light and its color with SbCl3 reagent,
and its Rf value was almost identical with that of prednisolone. Oxidn. of 0.1 g. III 16 hrs. with HIO4 at room temp.
yielded 50 mg. 1,4-androstadiene-3,17-dione (VII), m. 135-7°, [α]20 D 112° (c 1, CHCl3), identical by mixed m.p. and
infrared absorption with the product prepd. by CrO2 oxidn. of 17α,21-dihydroxy-1,4-pregnadiene-3,20-dione. The
structure of the side-chain of III was established by the selective redn. of the 20-CO group according to Norymberski and
Woods (CA 50, 8702d). Thus, 17α-hydroxy-21-acetoxy-1,4-pregnadiene-3,20-dione (0.5 g.) was stirred 2 hrs. with 80
mg. NaBH4 at 3°; the resulting mixt. concd. in vacuo, acidified, and extd. with CHCl3 left a solid residue from the ext.,
which was acetylated with Ac2O and C5H5N to yield 20 mg. V, identical to an authentic sample by mixed m.p. and
infrared absorption. The pos. shift in the mol. rotation produced by the acetylation of III to V indicated the β-orientation of
the 20-HO group. Thus, the structure of III was established. From these results it was concluded that I possessed
enzyme systems capable of performing ∆'-dehydrogenation, 11β-hydroxylation, and 20-hydrogenation. Production of IV
was a rare example of 11β-hydroxylation accomplished by microörganisms other than fungi. Ultraviolet absorption data
were reported. for III and V, and infrared data for III, V, VI, and VII.
~0 Citings
236. Plasticizers for cellulose esters

By Petzold, Werner; Rivier, Artur
From No Corporate Source data available (1960), DD 20137 19601019, Language: Unavailable, Database: CAPLUS
Acetylated monosalicylates of polyhydric alcs. are used, esp. for cellulose acetate. Thus, 1 mole glycerol monosalicylate
is treated with 3.3 moles Ac2O. After distn. of excess Ac2O and AcOH in vacuo, diacetyl glycerol monoacetylsalicylate is
obtained as an oil.
~0 Citings
237. Metallic zinc as a catalyst for quantitative acetylation of some hydroxy compounds
By Kyriacou, Demetrios
From Anal. Chem. (1960), 32, 291-2. Language: Unavailable, Database: CAPLUS, DOI:10.1021/ac60158a046
High-mol. hydroxy compds., such as poly(propylene glycol), 2,2'-thiobis(4-methyl-6-tert-butylphenol) and glycerol
monoricinoleate, are acetylated more rapidly in the presence of Zn. A procedure for poly(propylene glycol) is described,
and the mechanism is discussed.
~0 Citings
238. Glycerolysis of marine oils and the preparation of acetylated monoglycerides

By Gruger, Edward H., Jr.; Malins, Donald C.; Gauglitz, Erich J., Jr.
From Journal of the American Oil Chemists' Society (1960), 37, 214-17. Language: Unavailable, Database: CAPLUS,
DOI:10.1007/BF02632064
The glycerolysis reaction was applied to menhaden, tuna, herring, sardine, and salmon-egg oils. Optimum reaction time
for the prepn. of α-monoglycerides (I) was found to vary, reproducibly, from 45 to 60 min., depending on the particular
kind of marine oil employed. A lab. method for the prepn. of kg. quantities of highly pure acetylated I was developed.
Thin-layer silicic-acid chromatography was found suitable for the analysis of acetoglycerides from marine oils. 24
references.
~1 Citing
239. Aspects of stereochemistry. IV. Configuration and some reactions of the 1,3-O-benzylideneglycerols (5-
hydroxy-2-phenyl-1,3-dioxanes)
By Baggett, N.; Brimacombe, J. S.; Foster, A. B.; Stacey, M.; Whiffen, D. H.
DOI:10.1039/jr9600002574
cf. CA 54, 9787e. Configurations were allocated to the isomers of 1,3-O-benzylideneglycerol on the basis of the extent of
intramol. H bonding in dil. CCl4 solns., which affected the conformational stability and reactivity of certain cyclic acetals.
Whereas acylation and etherification of cis-1,3-O-benzylideneglycerol (I) yielded cis derivs., the trans isomer (II) yielded
mixts. of cis- and trans derivs. Equilibration with (iso-PrO)3Al revealed the cis isomer as the more stable, whereas the
trans-2-O-benzyl ether was the more stable when it was equilibrated with its isomer by acid. II had a greater affinity than
I for Al2O3 in chromatography; of esters and ethers the cis compds. were the more strongly adsorbed. I, m. 79.5-80.5°,
was obtained in 20% yield and recrystd. from C6H6-ligroine. Redistd. glycerol (121 g.), 106 g. BzH, and 5 drops concd.
H2SO4 were heated 1 hr. at 100° at 10, 4, and 25 mm.; 0.60 mole H2O distd. The mixt. stored 2 days at 0° gave 17 g. I
and fractions (A), 11.5 g., m. 60-3°, and (B), 9 g., m. 63-5°. Chromatography showed that A contained 75% II and 25% I.
On chromatography on Al2O3 of artificial mixts. of I and II, the I emerged first with C6H6-Et2O and II only with a more
polar solvent. The pure isomers did not isomerize on Al2O3. A continuous stream of air was drawn through a mixt. of
200 g. BzH, 220 g. glycerol, and 10 drops concd. H2SO4 at 95°, 275 ml. C6H6 added, and the H2O removed
azeotropically. The product collected, freed of acid, and crystd. gave 111 g. I and 92.9 g. mixt. of I and II. I or II (0.5 g.),
0.1 ml. Me2CO, and 0.5 g. (iso-PrO)3Al in 10 ml. iso-PrOH was refluxed 4.5 days, poured into 100 ml. N NaOH, extd. with
Et2O, and chromatographed on Al2O3. In this way II gave 0.429 g. product from which 0.244 g. I and 0.15 g. II were
recovered. Similarly, I gave 18% II and 59% I. I (1 g.) in 24 ml. C6H6 refluxed 36 hrs. with 0.3 g. Na, then refluxed 16
hrs. with 1.4 g. PhCH2Br, the cooled soln. washed, dried, and evapd. gave 0.74 g. 2-O-benzyl-cis-1,3-O-
benzylideneglycerol (III), m. 75.5-6.5° (ligroine). In 2 parallel expts., PhCH2Br was stored over anhyd. K2CO3 and the
products chromatographed to give only III. Replacement of the Na with NaH gave a 13-32% yield of III, whereas the use
of NaNH2 gave about 50% yield. II (0.5 g.) treated as above with 0.12 g. NaNH2 and 0.7 g. PhCH2Br and
chromatography of the 0.45 g. crude product gave 0.27 g. 2-O-benzyl-trans-1,3-O-benzylideneglycerol (IV), m. 91-2°
(ligroine). IV emerged first on elution with ligroine. The III (21%) was eluted with a more strongly polar solvent. IV did
not isomerize during chromatography on Al2O3. Benzylation of 0.5 g. II with Na and PhCH2Br as above gave 50% IV and
36% III. II was recovered unchanged after treatment with Na and C6H6. IV (2 g.) in 24 ml. MeOH and 8 ml. 4N HCl
refluxed 1 hr., cooled, dild. with H2O, freed from BzH, and the mixt. extd. with CHCl3 gave 49% 2-O-benzylglycerol (V),
b0.05 140°, m. 38-40°. Similar hydrolysis of III gave 70% V. Hydrolysis of III by p-nitrophenylhydrazine gave 3.9% V.
Attempts to hydrogenolyze selectively the benzyl group in III were unsuccessful. III (1 g.) hydrogenated in the presence
of 2 g. Pd-C in 35 ml. MeOH gave only glycerol, isolated as the tris(naphthylcarbamate), m. 191-2° (alc.). A soln. of
chromatographically homogeneous 2-O-benzyl-1,3-O-benzylideneglycerol (0.1 g.) in 10 ml. dry C6H6 was stored 66 hrs.
at 50° under anhyd. conditions, then washed with NH4OH, and evapd. and the residue chromatographed on Al2O3 to
give the following results. III gave 73% IV and 33% III. IV gave 66% IV and 35% III. II (0.2 g.) in 0.245 g. C5H5N treated
13 hrs. at 18° with 0.2 g. Ac2O, poured into ice H2O, the ppt. dissolved in CHCl3, washed, evapd., and then
chromatographed on Al2O3 gave 0.028 g. 2-O-acetyl-trans-1,3-O-benzylideneglycerol (VI), m. 115-16°. The cis-O-
acetate (VII) (0.134 g.) was eluted with a more polar solvent mixt. VI was not isomerized by chromatography. The ratio
of VII:VI in the above expt. was 4.8:1. In sep. expts. at 40°, VI was treated in 1 case with an acetylating mixt. equal to
that described above and in the other case the same mixt. supplemented by a small amt. of 0.02N HCl in C6H6.
Although no VII was detected by chromatography, VI could be recovered in only 50% yield. I (0.2 g.), 0.242 g. C5H5N,
and 0.2 g. Ac2O stored at 18° and chromatographed on Al2O3 revealed only VII, m. 100-1° (C6H6ligroine). Attempts to
equilibrate the acetates in C6H6 contg. dry HCl were unsuccessful. A soln. of chromatographically homogeneous VII
(0.187 g.,) in 5 ml. dry MeOH treated 1 day with Na, treated with H2O, neutralized, filtered, evapd., and chromatographed
on Al2O3 gave only I. Under the same conditions, 0.125 g. VI gave a crude product which contained only a trace of II.
Sep. solns. of 100 mg. of I or II in 50 ml. 0.02N H2SO4 were kept at 35° and the glycerol content in aliquot parts was
detd. after neutralization with NaHCO3 by periodate; both I and II yielded glycerol at approx. the same rate; the following
was a typical result (time in min., and % hydrolysis given): 3, 13; 5, 16.5; 10, 35.5; 15, 45; 20, 55; 30, 71; 45, 83.5; 61,
91; 76, 99.
~10 Citings
240. Amino sugars. IV. Imidazole derivatives from [N-substituted] 1-amino-1-deoxy-D-fructose

By Huber, G.; Schier, O.; Druey, J.
From Helvetica Chimica Acta (1960), 43, 1787-95. Language: German, Database: CAPLUS
cf. CA 55, 23353b. 1-Deoxy-1-(p-toluidino)-D-fructose (I) (5.4 g.), 6.1 g. KNCO, and 40 ml. N HOAc was heated 2 hrs.
on the steam bath, kept at 0°, and the crystals recrystd. from 50% aq. EtOH to give 4.3 g. 4-D-arabino-tetrahydroxybutyl-
1(p-tolyl)-4-imidazolin-2-one, m. 186-7°, [α]22 D - 16° (c 1.08, C5H5N). I (10.8 g.), 9.1 g. NH4SCN, and 60 ml. N HOAc
heated 2.5 hrs. on the steam bath and the soln. kept 24 hrs. at 0° gave 10 g. cryst. 1-[2-mercapto-1-(R-substituted)-4-
imidazolyl]-D-arabino-tetritol (II) (R = p-tolyl) (III), m. 205-7° (50% aq. EtOH), [α]21 D -33° (c 0.73, C5H5N). Similarly
prepd. in 60-70% yields were II, R was p-acetamidophenyl (IV), benzyl (V), p-chlorophenyl (VI), p-ethoxyphenyl (VII), p-
hydroxyphenyl (VIII), Ph, o-tolyl (IX), and 1,2,4-Me2C6H3 (X) [R, m.p., and [α]D (C approx. 1, C5H5N) given]: IV, 247-9°, -;
V, 180-2°, -27.4°; VI, 188-9°, -; VII, 214-15°, -; VIII, 199-200°, -30°; Ph, 179-81°, -; IX, 214-6°, -30.5°; and X, 202-4°, -30°.
II (R = III) (6.2 g.), and 50 ml. 0.4N KOH-MeOH shaken 15 min., evapd., 14.1 g. MeI and 50 ml. abs. C6H6 added, the
mixt. shaken 1 hr. at room temp., stirred 5 hrs. under reflux, evapd., and the solid crystd. from H2O gave 4.8 g. 1-[2-(R'-
substituted-thio)-1-(R-substituted)-4-imidazolyl]-D-arabino-tetritol (XI, R = III, R' = Me), m. 177-8° (H2O), [α]27 D -14° (c
0.946, C5H5N). Similarly prepd. in 70-90% yields were the related XI [R, R', m.p., and [α]D (c approx. 1, C5H5N) given]:
III, Et, 189-90°, -14°; III, NCCH2, 206-7°; III, allyl-0.5H2O, 170-1°, -15.8°; III, iso-Pr, 137-8°, -; III, Bu-H2O, 98-9°, -; III,
lauryl, 100-2°, -13.7°; IV, NCCH2, 219-20°, -; V, NCCH2, 120-22°, -20.5°; VI, NCCH2, 217-18°, -; VII, Me, 1701°, -7.8°;
VII, Et, 173-4°, -11°; VII, NCCH2, 196-8°, -8°; VIII, NCCH2, 162-3°, -19°; X, NCCH2, 192-3°, -19°; and Et, NCCH2, 178-
80°, -59.7°. II (R = III) (6.2 g.), 4.4 g. ethylene oxide. 50 ml. 50% aq. EtOH, and 1 drop N HCl shaken overnight at room
temp., evapd. in vacuo, and recrystd. from EtOH gave 6.4 g. 1-[2-(2-hydroxyethylthio) - 1 - (p-tolyl)-4-imidazolyl]-D-
arabino-tetritol, m. 165-6°, [α]26 D -17.5° (c 1.317, C5H5N). Similarly prepd. in 60-90% yields were the corresponding 2-
[S-(2HOC2H4)] derivs. [R, m.p., and [α]D (C approx. 1, C5H5N) given]: IV, 200-201°, -8.7°; VI, 184-5°, -13.9°; VII, 160-1°,
-11.2°; IX, 178-9°, -14.5°; and X, 137-8°, -11.4°. II (R = III) (6.2 g.), 4.3 g. ethylenimine, 50 ml. 50% aq. EtOH, and 1 drop
N HCl stirred 5 hrs. under reflux, evapd. in vacuo, and recrystd. from EtOH gave 3.9 g. 1- [2-(2-aminoethylthio )-1-(p-
tolyl)-4-imidazolyl]-D-arabinotetritol, m. 158-9° (EtOH). XI (R' = Me, R = III or VII) (10 millimoles), 30 ml. HOAc, and 6.8
ml. 30% aq. H2O2 kept 5 hrs. at 50-60°, evapd. in vacuo, and the product crystd. from EtOH gave 50% Me 4-D-arabino-
tetrahydroxybutyl 1-(R-substituted)-2-imidazolyl sulfone (R = III), m. 181-3°, and product (R = VII), m. 183-5°. II (10
millimoles) in 5 ml. H2O and 2 ml. HNO3 kept 1.5 hrs at 45-50°, evapd. in vacuo below 40°, and crystd. from EtOH gave
∼65% H2SO4 salts of 1-[1-(R-substituted)-4-imidazolyl]-D-arabino-tetritol (XII) [R, m.p., and [α]D (C approx. 1) given]: III,
195-7°, -; IV-0.5H2O, 189-90°, -; VI, 193-4°, -; VII, 187-9°, -5.35° (C5H5N); IX, 192-4°, -; and X, 180-2°, -20.3° (H2O). XII
(R = III).H2SO4 (3.76 g.) in 20 ml. N NaOH warmed until dissolved, the soln. evapd. in vacuo, and the solid crystd. from
H2O gave 1.25 g. XII (R = III), m. 185-7°; HNO3 salt, m. 153-5°. XI or XII (10 millimoles) dissolved in 20 ml. HOAc, 30
millimoles Pb(OAc)4 in 100 ml. HOAc, added, the mixt. kept 10 min. at room temp., excess H2S passed, the mixt. filtered,
the filtrate evapd. in vacuo, and the residue crystd. from EtOH gave 60-70% 1,2-RR'-substituted-4-formylimidazole (XIII)
(R, R'' and m.p. given): III, H, 150-2°; III, MeS, 115-17°; III, Me sulfone, 128-30°; III, NCCH2S, 184-5°; IV, 2-HOC2H4S,
160-2°; VI, H, 186-7°; VI, 2-HOC2H4S, -; VII, H, 137-8°; VII, MeS, 118-20°; VII, EtS, 88-90°; VII, 2-HOC2H4S, 137-9°; and
X, H, 110-12°. Alternatively, to 10 millimoles XI or XII was added 33 millimoles NaIO4 in 100 ml. N HOAc, the mixt.
cooled in ice, stirred 1.5 hrs., 0.5 ml. glycerol added, stirred 1 hr. with cooling, 2N NaOH to pH 7-8 added, the mixt. extd.
with CHCl3, the ext. washed (satd. NaHCO3), dried (Na2SO4), evapd. in vacuo, and crystd. from EtOH to give 70-80%
XIII. II (R = III) (10 millimoles) in 20 ml. C5H5N and 100 millimoles Ac2O kept 1 day at room temp., poured into ice H2O,
extd. with CHCl3, the ext. washed (H2O and satd. NaHCO3), dried (Na2SO4), evapd. in vacuo, and crystd. from a little
EtOH gave 2.36 g. tetra-O-acetyl-S-acetyl deriv. of II (R = III), m. 90-2°. Similarly acetylated, 3.24 g. XI (R = III, R' = Me)
gave 3.62 g. tri-O-acetyl deriv. (presumably having an O ring from C-5 of the imidazole ring to C-3 of the
tetrahydroxybutyl chain), m. 101-2°, [α]27 D -55.7° (c 1.004, C5H5N). II (R = III) (3.1 g.), 11.5 ml. PhCH2Cl, and 25 ml.
dioxane stirred, 5.6 g. KOH added, the mixt. cooled to keep the temp. at 80-90°, stirred 3 hrs. at that temp., steamdistd.
to remove excess PhCH2Cl, extd. with CHCl3, the ext. washed (H2O and satd. NaHCO3), dried (Na2SO4), and evapd. in
vacuo gave 6.73 g. tri-O-benzyl-2-(S-benzyl) deriv. (presumably having the above-mentioned ring), yellow oil, [α]28 D -
17.1° (c 1.255, CHCl3).
~2 Citings
241. Synthetic furocoumarins. I. New synthesis of methylsubstituted psoralens and isopsoralens

By Kaufman, Kurt D.
DOI:10.1021/jo01060a028
Claisen rearrangement of 7-allyloxycoumarins to 8-allyl-7-hydroxycoumarins followed by acetylation, bromination, and
cyclization in a basic medium yielded I and II. 7-Allyloxy-4-methylcoumarin (48 g.) was heated 2 hrs. in a closed vessel
at 215-20° to yield 94% 8-allyl-7-hydroxy-4-methylcoumarin, m. 198-9°, acetylated by refluxing 5 hrs. in 350 ml. Ac2O
with fused NaOAc to give 74% 7-acetoxy deriv., m. 87-7.5°, and brominated (25.80 g.) in 200 ml. AcOH with 16 g. Br to
give 95% crude 7-acetoxy-8-(2,3-dibromopropyl)-4-methylcoumarin, m. 156-7° (alc.). The Br compd. (30.00 g.) and
40.30 g. KOH in 1 l. alc. refluxed 2 hrs. yielded 60% II (R = Me), m. 182-3°. Similarly, Claisen rearrangement of 9.00 g.
7-allyloxycoumarin gave 78% 8-allyl-7-hydroxycoumarin, m. 165-6° (alc.), acetylated to 80% 7-acetoxy deriv., m. 93-3.5°
(ligroine), brominated quant. to 7-acetoxy-8-(2,3-dibromopropyl)coumarin, m. 123-3.5° (MeOH), and cyclized to give 51%
II (R = H), m. 153-4° (MeOH). The method was also applied to the synthesis of I with a Me group blocking the reactive 8-
position. H2C(CO2H)2 (20.80 g.), 15.20 g. 3,2,4-Me(OH)2C6H2CHO, and 2 ml. PhNH2 (distd. from Zn dust) kept 48 hrs.
at 40-5° in 80 ml. C5H5N yielded 92% 7-hydroxy-8-methylcoumarin-3-carboxylic acid, m. 258-9° (decompn.) (AcOH).
The product (9.60 g.) refluxed 1 hr. in 100 ml. freshly distd. glycerol gave 7-hydroxy-8-methylcoumarin, m. 258-9°,
converted by refluxing 16 hrs. with 23.50 g. anhyd. K2CO3 and 16.8 ml. H2C:CHCH2Br in 500 ml. Me2CO to 87% 7-
allyloxy-8-methylcoumarin (III), m. 125-5.5°. III (5.58 g.) heated 75 min. at 215-20° yielded 80% 6-allyl-7-hydroxy-8-
methylcoumarin, m. 153-40 (alc.), acetylated to 80% 7-acetoxy deriv., m. 119-19.5°, brominated quant. to 7-acetoxy-6-
(2,3-dibromopropyl)-8-methylcoumarin, m. 129-30° (alc.), and cyclized to 49% I (R = H), m. 176-7°. Claisen
rearrangement of 195.0 g. 7-allyloxy-4,8-dimethylcoumarin gave partially moist 6-allyl-7-hydroxy-4,8-dimethylcoumarin
(after heating 6 hrs. at 70°), acetylated with 915 ml. Ac2O to 64% 7-acetoxy-6-allyl-4,8-dimethylcoumarin, m. 144.5-5.5°
(alc.). The acetoxy compd. (145.4 g.) in 800 ml. CHCl3 treated below 25° with regulated addn. of 85.2 g. Br in 200 ml.
CHCl3 gave 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin, m. 141.5-2.5°. The bromo compd. (245.7 g.)
refluxed 1.75 hrs. in 2.1 l. abs. alc. (dried over Mg) contg. 65.4 g. Na gave 48% I (R = Me), 234.5-5°. The necessity of
using blocked 7-allyloxycoumarins was avoided with partial success by effecting the Claisen rearrangement prior to
forming the coumarin ring system. Anhyd. K2CO3 (138.2 g.), 101.3 g. 3-AcOC6H4OH, and 181.5 g. H2C:CHCH2Br
refluxed 24 hrs. on a steam bath in 300 ml. Me2CO yielded 82% 3-AcOC6H4OCH2CH:CH2 (IV), b0.05 82°, giving a faint
red-brown color with alc. FeCl3. IV (60.2 g.) in 100 ml. PhNEt2 refluxed (N atm.) 50 min. yielded 73% oil, b0.1 98°, n17D
1.5360, giving an intense red-brown color with FeCl3 in alc., and consisting of a mixt. (V) of 2-allyl- and 4-allyl-resorcinol.
V (5.00 g.) in 50 ml. AcOH contg. 4.33 g. AcCH2CO2Et satd. with dry HCl, kept overnight and poured into H2O, the solid
taken up in Et2O, extd. with 5% NH4OH and acidified gave 407 g. colorless prisms, m. 137-60°, repeatedly crystd. from
alc. to give 0.035 g. 8-allyl-7-hydroxy-4-methylcoumarin, m. 198-9°. The mother liquors dild. with H2O gave 4.01 g. white
solid, acetylated (1.151 g.) with NaOAc and Ac2O to give 1.125 g. material, chromatographed on acid-washed Al2O3 to
yield 0.050 g. 7-acetoxy-6-allyl-4-methylcoumarin (VI), m. 135-6°, 0.25 g. 8-allyl-7-hydroxy-4-methylcoumarin, and 0.23
g. 6-allyl-7-hydroxy-4-methylcoumarin, m. 174-5°, acetylated to yield VI. VI (0.119 g.) brominated in AcOH gave 7-
acetoxy-6-(2,3-dibromopropyl)-4-methylcoumarin, m. 150-1°. The bromo compd. (0.155 g.) cyclized with alc. KOH
yielded 55% 6-hydroxy-2-methyl-5-benzofuran-β-methylacrylic acid 8-lactone, m. 161-2°.
~18 Citings
242. Synthesis of 4-O-(β-D-glucopyranosyl)-D-ribitol, a degradation product of the ribitol teichoic acid from the
walls of Bacillus subtilis
By Baddiley, J.; Buchanan, J.; Hardy, F. E.
DOI:10.1039/JR9610002180
cf. CA 54, 6878a, 22820i. Koenigs-Knorr condensation of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (I) with 5-
O-benzyl-2,3-O-isopropylidene-1-O-trityl-D-ribitol (II) followed by removal of the blocking groups gave 4-O-(β-D-
glucopyranosyl)-D-ribitol (III), identical with the product prepd. by degradation of the ribitol teichoic acid from B. subtilis
cell wall (loc. cit.). Tritylation of 2,3-O-isopropylidene-D-ribitol (IV) (Hough, et al., CA 53, 13068e) gave 80% 1,5-ditrityl
ether (V) of IV, m. 170-1° (EtOH), [α]24 D 17.2° (c 4.1, C6H6), benzoylated to 4-benzoate of V, m. 87-9° (EtOH).
Condensation of V with I in C6H6 contg. Ag2CO3, CaSO4, and iodine followed by sapon. of the product gave a 76% return
of V. Mild acid hydrolysis of the remainder, followed by C-Celite chromatography gave (papergram) ribitol, and low yields
of 2 other sirupy compds. with Rribitol 0.58 and Rribitol 0.50 (40:10:49:1 BuOH-EtOH-H2O-NH4OH solvent system). The
former corresponded to III. Both compds. were hydrolyzed by β-glucosidase, and gave glycerol and (CH2OH)2 after
periodate oxidn., NaBH4 redn., and acid hydrolysis, which suggested that the former compd. was III, and the latter
probably 1-O-(β-D-glucopyranosyl)-D- or L-ribitol. 2,3-O-Isopropylidene-D-ribono-1,4-lactone (1 g.) in 30 ml. HCONMe2
was stirred 16 hrs. with 5.5 ml. PhCH2Br and 6 g. Ag2O to give, after silicic acid chromatography, 1.4 g. 5-O-benzyl-2,3-
O-isopropylidene-D-ribono-1,4-lactone (VI), b0.00001 125-35°, n22 D 1.5065, [α]23 D -39.6° (c 1.1, EtOH). Treatment of VI
with cyclohexylamine at 100° gave 5-O-benzyl-N-cyclohexyl-2,3-O-isopropylidene-D-ribonamide, m. 63-5° (petr. ether).
Redn. of 1 g. VI with LiAlH4 in tetrahydrofuran gave 1 g. sirupy 5-O-benzyl-2,3-O-isopropylidene-D-ribitol (VII), Rf 0.9 in
5:1:4 BuOH-EtOH-H2O solvent system. Hydrogenation of VII over Pd gave only IV (papergram). Tritylation of VII gave
sirupy II, which was acetylated with Ac2O-C5H5N to give 54% 4-acetate (VIII) of II, m. 112-14°. Sapon. of 0.32 g. VIII
with NaOMe-MeOH gave 0.28 g. cryst. II, m. 53-5° (MeOH), [α]22 D 20.3° (c 4.1, C6H6). II (2 g.), 3 g. Ag2CO3, 7 g.
CaSO4, and 30 ml. C6H6 were shaken together, 1.8 g. I and 0.35 g. iodine were added, and after 80 hrs. shaking the
product was sapond. with NaOMe and chromatographed on neutral Al2O3. Elution with C6H6 and C6H6-CHCl3 gave 0.35
g. sirupy II, hydrogenated over Pd and tritylated to give 0.28 g. V, m. 170-1°, [α]22 D 17.5° (c 3, C6H6), which indicated
that II was not isomerized during the condensation reaction with I. Elution with 95:5 CHCl3-MeOH gave 0.2 g. 5-O-
benzyl-4-O-(β-D-glucopyranosyl)-2,3-O-isopropylidene-1-O-trityl-D-ribitol, m. 80-2° (petr. ether), which was hydrogenated
over Pd, heated with a mixt. of 2.5 ml. N H2SO4 and 47.5 ml. EtOH 45 min., and deionized, to give 20 mg. III, m. 134-7°
(MeOH-Et2O), [α]22 D -22° (c 1, H2O). Acetylation of III with Ac2O-C5H5N gave III octaacetate, m. 100° (EtOH), [α]22 D -
14.1° (c 1.5, CHCl3). Hydrolysis of III with 2N HCl 9 hrs. at 100° gave anhydroribitol, glucose, ribitol, and traces of acid
reversion products (papergram).
~3 Citings
243. Prothrombin activation with trypsin as enzyme

By Landaburu, Ricardo H.; Barnhart, Marion I.; Seegers, Walter H.
From American Journal of Physiology (1961), 201, 298-302. Language: Unavailable, Database: CAPLUS,
DOI:10.1152/ajplegacy.1961.201.2.298
cf. CA 54, 11227d. Prothrombin activation with trypsin only involves a random type of proteolysis in which thrombin yield
is small. In the presence of glycerol or certain lipids of interest in blood coagulation and classified as procoagulants,
proteolysis of prothrombin with trypsin is made more specific and the thrombin yield is high. Trypsin-thrombin was
isolated by chromatography on cellulose. Its sedimentation const. was approx. the same as for other thrombin prepns.
Both terminal amino acids were arginine. Acetylated prothrombin was not activated with trypsin. Under appropriate
conditions the activation of prothrombin in the presence of trypsin is a zero-order reaction.
~0 Citings
244. Partial periodate oxidation of D-glucitol and its borate complex

By Hutson, D. H.; Weigel, H.
DOI:10.1039/jr9610001546
The products of oxidn. of D-glucitol (I) with 0.25 mole NaIO4 (II) per mole were characterized and detd. The order of
susceptibility of cleavage of the C-C bonds of I was 3,4 > 2,3 > 4,5 > 5,6 > 1,2. In the most stable complex of I with
borate (III), III engaged the OH groups at C-2 and C-4 of I; suitable oxidn. with II, of the complex gave 30% L-xylose (IV).
To (a) 1 molar proportion 0.166M I, or a mixt. thereof with 3 molar proportions (b) 0.5M III buffer of pH 10.6 (V) or (c)
0.5M phosphate buffer of pH 10.1 (VI) was added 0.25 molar proportion II soln., the mixt. kept 10 min., Amberlite IR-
120(H+) (VII) added with stirring to pH 5, and the products identified and detd. (% for a, b, and c): I, 75.00, 91.20, 89.80;
D-arabinose (VIII), 0.42, 0.66, 0.42; IV, 0.75, 1.75, 0.92; D-erythrose (IX), 3.13, 2.00, 0.53; L-threose (X), 1.00, 0.07, -;
DL-glyceraldehyde (XI), 13.45, 0.75, 1.86; glycolaldehyde (XII) 2.83, 2.40, 2.73; CH2O, 0.25, 0.27, 0.20; HCO2H, 0.08,
0.70, 1.30. I, IV, VIII, and XI were identified on papergrams with 5:1:3:2 BuOH-C6H6-C5H5N-H2O (XIII) and with 9:2:2
EtOAc-HOAc-H2O (spray of Me2COAgNO3-alcoholic NaOH or p-MeOC6H4NH2.HCl in BuOH); IX and X were sepd. by
papergrams with H2O-satd. 2-butanone (XIV) and identified by paper ionophoresis (molybdate soln.); XII was identified
by a peak at 680 mµ after treatment with Ph2NH-HOAc; CH2O was revealed by the chromotropic acid method; and
HCO2H was assumed to be the total titratable acid. For detn. of I, IV, and VIII, D-glucitol-C14 (IA; A = uniformly labeled
with C14) was oxidized as for I, I, IV, or VIII added, the soln. kept overnight, III removed by repeated distn. with MeOH, IV
removed by pptn. with Ba(OH)2, and the product sepd. by chromatography on Whatman paper No. 3 with XIII. IA was
acetylated and the hexaacetate recrystd. (EtOH) to const. m.p. and sp. radioactivity. IVA and VIIIA were converted to
their Ph osazones, which were recrystd. from H2O (twice) and C6H6 (twice) to const. m.p. and sp. activity. For detn. of IX
and XI, the soln. from oxidn. of IA was treated 12 hrs. with KBH4 at room temp. and then with VII, erythritol (XV) added
and then glycerol (XVI), the mixt. kept 1 hr., III removed as before, XVA and XVIA sepd. on paper No. 3 with 4:1:5 BuOH-
EtOH-H2O (org. phase), benzoylated, and the resp. tetra- and tribenzoate recrystd. from aq. C5H5N and aq. EtOH, resp.,
to const. m.p. and sp. activity. For detn. of X, 20 mg. IA was oxidized (methods a and b), the soln. treated with VII, and
III removed as before; IXA and XA were sepd. by a papergram with XIV, and the eluted tetroses ionophoresized in
molybdate (pH 5); the positions of IXA and XA were revealed by p-MeOC6H4NH2.HCl in BuOH and ultraviolet light, and
comparison of the β-emission of the 2 spots gave the ratio of IXA to XA. The yield of XA was calcd. from the yield of IXA
(above). For detn. of XII, 0.91 g. I was oxidized (methods a, b, c), the soln. was freed from iodate with Amberlite IRA-400
(OAt) (if III was present, much I was first added), and colorimetric detn. (Ilford filter No. 608) showed 0.085 (a), 0.072 (b),
and (c) 0.082 mole XII per mole I. For detn. of CH2O, 0.91 g. I was oxidized, and CH2O was steam-distd. and detd.
(Ilford filter No. 606) to be 0.015 (a), 0.016 (b), and 0.012 mole (c) CH2O per mole I. For detn. of HCO2H, 0.91 g. I was
oxidized, and (for b and c) the soln. was acidified and the HCO2H distd.; titration (pH meter) with 0.01N NaOH then
showed 0.005, 0.042, and 0.078 mole HCO2H/mole I (after subtraction of a blank titer given by oxidn. of ethylene glycol
with 0.125 molar proportion II). The ratios of yield of IV and VIII by methods b and c were resp. 2.3 and 1.2 times that for
a, showing that presence of III increased the yield of IV. To a soln. of 1.82 g. I in 12.5 ml. 4M III (pH 10.7) was added
5.45 g. II in 25 ml. H2O, the soln. kept 10 min., treated with VII, the soln. evapd., the residue repeatedly evapd. with
MeOH, and the residue extd. with MeOH. A papergram with XIII showed a major component of Rf of IV, and elution and
quant. detn. (anthrone method) showed 30.6% IV.
~1 Citing
245. Membranes for the electrophoretic separation of mixtures

By Maier, Karl Heinrich; Grassmann, Wolfgang
CAPLUS
The films are made by combining cellulose acetates of low and high degree of acetylation in proportions of 9-1: 1, esp. 3-
2:1. The primary solvent is CH2Cl2, optionally with BuOH; the secondary solvent is iso-BuOH. Small amts. of glycerol
and wetting agents are added. High transparency is obtained by increasing the d. of the film. Thus, 18 g. cellulose
acetate of 53.5% AcOH and 10 g. of 61% was dissolved in CH2Cl2 360 and BuOH 40, and iso-BuOH 200, glycerol 7 ml.,
and 0.2 g. wetting agent were added. The film cast on glass or metal was white and had a pore vol. of 80-5%. After
swelling with AcOH and MeOH, a highly transparent film was obtained. It is esp. useful for sepg. the protein fractions in
serums.
~0 Citings
246. Lactone adducts

By Fowler, George W.; Carruthers, Thomas F.
CAPLUS
ε-Caprolactone (I) (228 g.) was treated with 438 g. HOCH2CHEtCHPrOH (II) and 2 ml. HO2CCHEtBu (III) at 144-80° for
6.75 hrs. and the mixt. distd. to give 256 g. II and 406 g. residue (IV), colorless liquid, acidity 0.0072 ml. N base/g. OH
value 10%, sapon. equiv. 207.1, n30 D 1.4618. IV (300 g.) was acetylated with 270 g. Ac2O 3 hrs. at 125° to give 372 g.
acetyl ester, acidity 0, OH value 0, n30 D 1.4473, mol. wt. 415. IV (500 g.), 375 g. III, and 3 ml. alkanesulfonic acid were
refluxed in PhMe for 13.5 hrs. as the H2O was taken off in a trap, the residue neutralized with alc. KOH, stripped to 210°
at 3 mm., and steamed 2 hrs. at 160-77°/40-50 mm. to give a liquid, Gardner color 11, acidity 0.126 ml. N base/g., sapon.
equiv. 160, mol. wt. 600. Similarly were prepd. (alcohol, acylating agent, Gardner color, acidity in ml. N base/g., %
hydroxyl value, viscosity in cp., mol. wt., b.p./pressure, sapon. equiv., n30 D, d20 20 and % yield given): (HOCH2)3CEt,
Ac2O, 8, 0.228, 0, 540, 770, --, --, --, --, --; glycerol, Ac2O, 8, 0.0678, 0, 500, 830, --, --, --, --, --; II, azelaic acid (V), 8,
0.1285, 1.51, 6000, 1575, --, --, --, --, --; (HOCH2)2, pimelic acid (VI), 4, 0.275, 1.24, 5200, 1815, --, 111.9, --, --, --;
HOCH2CHMeOH, V, 6, 0.299, 0.31, 17,500, 2365, --, --, --, --, --; II, adipic acid (VII), 7, 0.0452, 0.78, 32,000, 2390, --, --,
--, --, --; HOCH2CHEtBu (VIII), --, 1, 0.017, 4.02, --, 442, --, --, 1.4552, --, --; hexanol, --, --, --, --, --, --, 144--7°/2.5-3.1,
217, 1.4402,0.943, 71.5; C10 Oxo alcohol (IX), --, --, --, --, --, --, 153-60°/1.4-.5, 281, 1.4482, 0.952, 58.6; cyclohexanol, --,
0.04, 85, 7.2, --, --, 120-2°/1.5-3.0, 193, 1.4608, 1.0156, 48; HOCH2CH2OBu (X), --, --, 0.0566, --, --, --, --, 232, 1.4419,
0.945, 51.7; HOCH2CH:CH2, --, --, 0.0113, 9.7, --, --, 103-6°/1.5, 173, 1.4489, 1.0025, 53.7; 3-heptanol, --, --, --, 6.6, --, --
, 138°/2.5, 219, 1.4420, 0.940, 24.3; MeCH(OH)CH2CHMe2, --, --, 0.011, 8.0, --, --, 126°/2.5, 212, 1.4368, --, 10.6; VIII,
Ac2O, 1, 0.0888, 0.16, 96, --, --, --, --, --, --; VIII, phthalic anhydride (XI), 2, 0.003, --, 120, --, --, 500, 1.4789, 1.005, --;
VIII, VII, 2, 0.239, 0.20, 78, 560, --, --, --, --, --; hexanol, VI, 5, 0.160, --, 60, 580, --, 140, 1.4512, 0.996, --; X, XI, 9, 0.062,
--, --, --, --, --, 1.4772, 1.076, --; IX, CH2:CMeCO2H, 12, 0, --, --, --, --, 160, 1.4545, 0.970, --. Similar products were
obtained with mixts. of I with trimethyl-ε-caprolactone (prepd. from isophorone) and methyl-ε-caprolactone. The latter
mixt. was condensed with PhNH2 and acetylated to give a dark viscous liquid, acidity, 0.579, HO value 0. The adducts
were useful as plasticizers for vinyl resins, in polyurethan resins and as copolymers.
~5 Citings
247. Determination of guaiacol glycerol ethers in pharmaceutical preparations

By Wullen, Hedwige
From Archiv for Pharmaci og Chemi (1961), 68, 197-206. Language: French, Database: CAPLUS
Glycerol guaiacol ethers (I) can be detd. bromometrically by titration with Na2S2O3; they can also be detd. by the MeO
group according to Mathers and Pro (CA 50, 4724c); by acetylation and titration with NaOH to phenolphthalein; and by
colorimetry by heating with a reagent contg. 0.025 ml. 36% HCHO in H2SO4 at 50° for 1/2 hr. The color is measured at
540 mµ.
~0 Citings
248. Cyclic ethers of dialkylsilanediols and orthosilicic acid

By Davydova, V. P.; Voronkov, M. G.; Dolgov, B. N.
From Khim. i Prakt. Primenenie Kremneorg. Soedinenii, Trudy Konf., Leningrad (1961), (No. 6), 134-5. Language:
Tetraacyloxysilanes as acetylating agents could act in 2 different ways depending on temp. At higher temp., the ≡SiOAc
+ ROH → ≡SiOH + AcOR reaction took place, while at lower temp. ≡SiOR and AcOH formed. The same results were
obtained with diols. Me2Si(OAc)2 and glycerin gave Me2Si(OH)OCH2CH(OH)CH2OAc, which on standing deacetylated
and polymerized to [Me2SiOCH2CH(OH)CH2O]x. The gel-like H2O soluble polymer on distn. depolymerized to give a
fluid and on standing gelatinized again. Other cyclic ethers showed similar properties. All of them had a special
menthol-like odor.
~0 Citings
249. Cream shampoos

By Parran, John J.; Lang, Edward W.; Whyte, David D.
CAPLUS
Mixts. of Na alkyl glyceryl ether sulfonate (Na 3-alkoxy-2-hydroxypropanesulfonate) and Na N-lauroylsarcosinate with
inorg. Na salts, such as NaCl and Na2SO4, form an opaque shampoo with synergistic lathering properties. Thus, Na
coconut alkyl glyceryl ether sulfonate (contg. 23% diglyceryl ether sulfonate) 25, NaCl 6.7, Na2SO3 3.3, Na N-
lauroylsarcosinate 3.8, N-coconut fatty acyl sarcosine 1.2 with or without coconut fatty acid diethanolamine 2, acetylated
lanolin (Modulan) 1, perfume and color 0.44, phenyl Hg acetate 0.003% and H2O to make 100% formed an opaque
cream with a pH of 7. Cf. CA. 53, 9702g; Zussman and Lennon, CA 50, 8143a.
~4 Citings
250. Constitution of the galactomannoglycan from the kernel of green palmyra palm nut
By Mukherjee, A. K.; Choudhury, D.; Bagchi, P.
DOI:10.1139/v61-180
Methylation, fragmentation, and periodate oxidn. studies showed the title compd. (I) to have a β-D-(1 → 4)-linked
mannan backbone with one α-D-(1 → 6)-linked D-galactose unit side chain for each 2.4 D-mannose units; it thus
structurally resembled guaran and carob gum. Palm nut (Borassus flabellifer) kernels, homogenized with EtOH, gave 50
g. EtOH-insol. material which was heated 5 h. at 100° with 3 l. H2O, and the filtered, clarified soln. was poured into
acidified EtOH (pH 4-5) to ppt. 12, g. crude I, contg. D-galactose (II) and D-mannose (III) in the ratio 1:2.4. Crude I (10
g.) was purified by complexing with Fehling soln. giving 8.75 g. pure I, [α]30 D 9° (c 0.5, 4% NaOH soln.). Mild hydrolysis
of I with 0.04N H2C2O4 gave II only; the resulting degraded I contained a higher proportion of III. Total hydrolysis of I
with 72% H2SO4 8 h. at 100° gave II [p-O2NC6H4NH2 deriv. m. 217-18°, [α]30 D -245° (c 0.5, C5H5N)], and III [p-
O2NC6H4NH2 deriv. m. 217-18°, [α]30 D -325° (c 0.5, C5H5N)]. Methylation of 10 g. I (Falconer and Adams, CA 51,
1603d) gave 3.22 g. methylated I (IV), [α]29 D 28.7° (c 1, CHCl3), with mol. wt. 1.39 × 105 (light scattering). IV (1 g.) was
refluxed 15 h. with 4% MeOH-HCl, hydrolyzed with N HCl 14 h. at 100°, deionized with acidic ion-exchange resin, and
resolved by cellulose column chromatog. giving 245.7 mg. II 2,3,4,6-tetra-Me ether (V), [α]30 D 109° (c 1, H2O), a trace of
II 2,3,6-tri-Me ether, 277 mg. III 2,3,6-tri-Me ether (VI), [α]30 D -9° (c 1, H2O), and 212.9 mg. III 2,3-di-Me ether (VII), [α]30
D -16° (H2O). Demethylation of V with HBr gave II (papergram). V was heated with PhNH2 to give V PhNH2 deriv., m.
187° [α]30 D 38° (Me2CO). Demethylation of VI gave III; benzoylation of VI gave the 1,4-di-p-nitrobenzoate, m. 189-90°,
[α]30 D 32° (CHCl3). VII gave only III on demethylation and gave 2,3-di-O-methyl-D-mannonic acid phenylhydrazide, m.
158° [α]29 D -24° (H2O), on Br oxidn. and treatment with PhNHNH2. IV contained V, VI, and VII in the ratio 1:1.4:0.95. I
consumed 1.3 mol of periodate per hexose residue (30 h., const.), and liberated 1 mol of HCO2H per 3.7 hexose
residues (25 h., const.). Redn. of the periodate oxidized I with NaBH4 gave erythritol (tetra-p-toluenesulfonate, m. 163-
5°), and glycerol (tri-p-toluenesulfonate m. 102-3°), in the ratio 2.45:1. I (8 g.) in 100 mL. HCONH2 was acetylated by
addn. of 150 mL. C5H5N and 120 mL. Ac2O, the soln. was poured into H2O, the dried ppt. reacetylated similarly to give
6.8 g. acetylated I (VIII), [α]30 D 11° (c 1, CHCl3), intrinsic viscosity 5.65 dL./g. Fractionation of VIII by pptn. from 9:1 s-
tetrachloroethane-EtOH by addn. of MeOH gave 7 fractions with a II-III ratio rising successively from 1:2.6 to 1:3. The
fifth fraction of VIII (2 g.) was methylated in THF with Me2SO4 and NaOH, methanolyzed, and hydrolyzed giving V, VI,
and VII in the ratio 1:2.11:1.08 (papergram). Graded acid hydrolysis of 15 g. I with 0.4N H2SO4 2 h. at 100°, and further
hydrolysis of the insol. material 2 h. with 0.2N H2SO4, followed by neutralization with ion-exchange resin gave a mixt.,
resolved by cellulose-carbon and preparative paper chromatog. to give 243.7 mg. 4-O-β-D-mannopyranosyl-D-mannose
(IX), [α]30 D -8 → -7° (H2O), 114.7 mg. 6-O-α-D-galactopyranosyl-D-mannose (X), [α]30 D 124° (H2O), 48.3 mg. of a
trisaccharide (XI), [α]30 D 33° (c 1, H2O), contg. II and III in the ratio 1:2, and 82.6 mg. of a D-mannose trisaccharide (XII),
[α]30 D -15° (c 1, H2O). NaIO4 oxidn. of IX gave (time in hrs., molar oxidant uptake, molar HCO2H release): 10, 2.40,
1.35; 20, 3.90, 2.45; 30, -, 2.90; 35, 4.91, -. Redn. of the product with NaBH4 and hydrolysis gave glycerol and erythritol
(papergram). IX gave a phenylhydrazone, m. 198-99°. Hydrolysis of X gave II and III; redn. prior to hydrolysis gave II as
the only reducing sugar in the hydrolyzate. NaIO4 oxidn. of X gave (data as before): 10, 3.05, 1.95; 20, 4.75, 4.0; 30,
5.95, 4.93. NaIO4 oxidn. in pH 3.7 acetate buffer gave a 5.14 mol oxidant uptake (2.5 h., const.). Redn. and hydrolysis of
the oxidized product gave only glycerol. X phenylhydrazone m. 168-9°. Redn. and hydrolysis of XI showed a III residue
at the reducing end. In pH 3.7 acetate buffer XI consumed 6.12 mol periodate. XII had mol. wt. 488 (hypoiodite oxidn.)
and consumed 5.08 mol periodate in pH 3.7 acetate buffer.
~1 Citing
251. Chemical structure of the capsular polysaccharide from Cryptococcus neoformans

By Miyazaki, Toshio
From Chemical & Pharmaceutical Bulletin (1961), 9, 829-33. Language: Unavailable, Database: CAPLUS,
DOI:10.1248/cpb.9.829
II (14.6 mg.) was oxidized with 0.24M NaIO4 in 3% NaCl soln. Moles NaIO4 consumed and moles HCO2H and HCHO
produced were detd. according to A. and Tomoda (CA 50, 13225h). To det. the products of such oxidn. of I, the reaction
mixt. after 144 h. was reduced with NaBH4, followed by hydrolysis with 2N H2SO4. Paper chromatog. of the hydrolyzate
showed the presence of IV as the only reducing sugar, with some erythritol and glycerol. No III or V was detected.
These results showed the probability that IV constituted the branching points of I with 1,3- or 1,4-linkages, whereas III
and V were present as end groups, more easily attacked. For confirmation, II was methylated as completely as possible,
hydrolyzed, and the resulting methylated monosaccharides detd. II was methylated with Me2SO4 and NaOH at least 3
times, the partially methylated product further treated with Mci and Ag2O at least 8 times, and finally by alternate
acetylation with Ac2O-C5H5N and remethylation with Me2SO4 and NaOH or MeI and Ag2O until the product showed
43.3% MeO content. Hydrolysis of this with HCO2H, followed by N H2SO4 (as in the preceding part), passing the
neutralized hydrolyzate through Amberlite IR120, and subjecting the concd. simp to paper chromatog. and paper
electrophoresis showed the presence of 2,3,4-tri-O-methylxylose, 2,3,6-tri-O-methylmannose, 2,3, 4-tri-O-
methylglucuronic acid, and 3,6-di-O-methylmannose in 1:1:1:2 ratio. From all these results the chem. structure of I was
proposed as VI, where M = mannopyranose, X = xylopyranose, and GA = glucuronopyranose.
~2 Citings
252. Chemical structure of a phosphomucolipide and its occurrence in some strains of Salmonella
By Nowotny, A.
DOI:10.1021/ja01463a069
The chem. structure of the isolated, purified lipide was investigated in 6 strains. In view of the content of P (1.9-2.2%),
glucosamine (18.1-20.5%), and fatty acid (50-55%), this prepn. was called a phosphomucolipide. Approx. 65% of the dry
wt. became ether sol. after 10 hrs. of hydrolysis with 3N HCl in a boiling water bath. Of this, 86% consisted of free fatty
acid. About 50% of the dry wt. became water sol. after the hydrolysis. The H2O-sol. hydrolyzate analyzed by high
voltage paper electrophoresis contained a large amt. of glucosamine, [α]20 D +46.7°. Considerably smaller quantities of
aspartic acid, glutamic acid, alanine, serine, valine, arginine, and lysine and 3 ninhydrin-pos. compds. not identical with
known amino acids also were detected. These latter 3 compds. were 6-phospho-D-glucosamine, 4-phospho-D-
glucosamine, and 1-peptido-4-phospho-D-glucosaminide. The sequence was followed of appearance and
disappearance of the hydrolysis split products obtained with dil. HCl. Two possibilities exist for the linkage between the
D-glucosamine phosphate units: (a) direct linkages or (b) linkage through phosphodiester bridges. Alk. and acid
phosphatases failed to split free phosphoric acid from the lipides. Results with venom diesterase were obtained which
made (a) seem unlikely. Glycerol and sphingosine were not detected. Hydrazinolysis showed the amino acid group of
the glucosamine to be acetylated, approx. 30% of the total fatty acids being bound to amino groups. Thirty-five-45% of
the fatty acids are bound through labile ester linkages probably on the C-3 hydroxyl groups of the glucosamine. The
remainder probably is bound to C-6 forming a relatively stable substituent. The hydrolyzate of similarly isolated lipides
from Serratia marcescens, Pseudomonas aeruginosa, Escherichia freundii, E. coli 055, and Neisseria gonorrhoeae also
contained 4-phospho-D-glucosamine derivs.
~1 Citing
253. Chemical composition of enanthic esters and their effect on the quality of cognacs
By Gogichaishvili, E. A.
From Vopr. Biokhim. Vinodeliya (Moscow: Gos. Izd. Min. Prom.Prodovol'stv. Tovarov) Sb. (1961), 210-14. Language:
An enanthic ester, sp. gr. of 0.8767, refraction index 1.4300, acid no. 40.1, ester no. 261, and Lester no. after acetylation
4.9, was obtained from the yeast Rkatsitel No. 46 by steam distn. After saponification, caprylic, capric, lauric, myristic,
palmitic, and stearin acids were found in the acid part of the enanthic ester. After oxidn. in AcOH, EtOH and traces of
glycerol were found in the alc. part of the ester. The yeast Candida pulcherima formed the most enanthic ester from
fermentation in Reeder's medium and in must; Sac-charornyces vini and Hanseniaspora apiculata followed in the order.
In an enanthic ester sepd. from cognac alc., the above-mentioned acids were found in a free state (35-40 mg./1.) and as
esters. The amt. of esters sepd. from cognac alc. varied from 50 to 80 mg./1. Freshly fermented wine material contained
5-15 mg./1. enanthic ester, the crude alc. 15-20, the 1st distn. fraction 120-180, the middle fraction 50-80, and the end
fraction 20-30. By adding different amts. of enanthic ester to cognac alc. followed by 3 months of aging, it was found that
the optimum dose of enanthic ester was 100 mg./1.
~0 Citings

254. Use of thin layer chromatography for following a glycerolysis reaction
By Rybicka, S. M.
From Chemistry & Industry (London, United Kingdom) (1962), 1947-9. Language: Unavailable, Database: CAPLUS
Thin-layer chromatography (TLC) (CA 56, 14423i) was applied to follow the glycerolysis reaction at 235°. A large(10 in.
× 10 in.) TLC plate coated with silicic acid plus 10% of plaster of Paris was used. Sym. and unsym, glycerides, were
sepd. completely when the TLC plate was developed in 40% Et2O in petr. ether mixt. The ratio of the concn. of 1,3-
diglycerides to that of 1,2-diglycerides was 1:4 and did not change during the reaction. The rates of formation of the
diglycerides was the same.
~0 Citings
255. Treatment of epoxy fatty compositions

By Findley, Thomas W.; Ohlson, John L.; Kuester, Frank E.
CAPLUS
Linear polyether polymers of fatty acids and derivs. can be prepd. from their epoxy derivs. Molten 9,10-epoxystearic acid
at 60° treated with 2% com. BF3-ether (I) reacted exothermically to yield a viscous oil, mainly the polyether polymer of
9,10-stearic acid, sol. in org. solvents and alkalies, useful as a lubricant additive. A partially epoxidized (1.3% oxirane O)
menhaden oil similarly polymerized is useful as a drying-oil since it can be air-dried to give a film. Epoxidized compns. of
stearates, esters of soybean oil fatty acid, or distd. acetylated monoglycerides of soybean oil can be similarly
polymerized by 0.5-2.0% I. Insol., infusible cross-linked polymers are produced when the fatty compn. treated with I
contains >1 epoxy group/mol. To prevent coating of I by polymer, a suitable Lewisbase solvent may be added to I.
Thus, when 10 ml. 2-methoxyethanol was added with stirring to 100 g. epoxidized soybean oil (6.2% epoxy O) contg. 1
ml. I. Solidification occurred after 19 sec. at 120° to give an elastic solid which could be ground to a powder of high
absorptive capacity. Epoxy derivs. of sperm oil, glyceryl trioleate, lard oil, linseed oil, menhaden oil, or rapeseed oil were
prepd.; sapon. gave the salts of the corresponding linear polymers; soaps of such polyether polybasic acids are useful as
surface active-agents. Alkoxyhydroxy or dihydroxy fatty esters can be obtained from epoxy fatty compds. by treating with
I in the presence of large amts. of alc. or H2O. The mole ratio of alc. to oxirane O should be <1, but greater than (n -1)/n,
where n is the no. of epoxy groups. To 1 part epoxidized soybean oil and 2 parts MeOH, 0.5-1% I was added. An
exothermic reaction occurred which, after washing with H2O and drying, yielded a mixed triglyceride of
hydroxymethoxystearic and dihydroxydimethoxystearic acid. A glyceride having a glycol configuration in the fatty acid
portion of the mol. was formed when 200 g. of epoxidized soybean oil and 50 g. H2O were mixed with 10 g. I and 100 ml.
dioxane at 60°.
~4 Citings
256. Thiosugars. I. Synthesis of derivatives of 2-amino-2-deoxy-1-thio-D-glucose

By Horton, D.; Wolfrom, M. L.
DOI:10.1021/jo01052a075
--A range of derivs. of 2-amino-2-deoxy-1-thio-D-glucose, with removable blocking substituents at the amino and thiol
groups, was synthesized by condensation of amino sugar glycosyl halides with CS(NH2)2 (I), KSAc (II), or KSCSOEt (III).
Thus, condensation of 6 g. 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-α-D-glucopyranosyl chloride (IV) with 6 g. I in boiling
Me2CO gave 82% 2-(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)-2-thiopseudourea-HCl (V), m. 179-81°
(decompn.) (MeOH-Me2CO), [α]22 D -29.2° (c 1.1, MeOH), complex rotatory dispersion. Similarly, condensation of 13.7
g. IV with 6.1 g. III in C6H6 gave, after Ac2O-C5H5N acetylation, 82% 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-
glucopyranosyl ethylxanthate (VI), m. 144-6° (EtOH-petr. ether), [α]24 D 33° (c 1.1, CHCl3), pos. Cotton effect.
Condensation of 10 g. IV with 3 g. II in Me2CO gave 53% 2-acetamido-3,4,6-tri-O-acetyl-1-S-acetyl-2-deoxy-β-D-
glucopyranose (VII), m. 199-200° (MeOH-Et2O), [α]23 D -2° (c 1.29, CHCl3), and 5% unidentified product, m. 136.0-7.5°
(MeOH-Et2O), [α]23 D 84° (c 0.4, CHCl3), possibly the anomer of VII. Desulfuriz0ation of V, VI, and VII with Raney Ni in
boiling EtOH with subsequent acetylation gave, in each case, 2-acetamido-3,4,6-tri-O-acetyl-1,5-anhydro-2-deoxy-D-
glucitol, m. 165-8° (EtOH-Et2O), in 82%, 86%, and 92% yields, resp. Treatment of 2-deoxy-2-(2,4-dinitroanilino)-D-
glucose in CHCl3 with AcBr gave 62% 3,4,6-tri-O-acetyl-2-deoxy-2-(2,4-dinitroanilino)-α-D-glucopyranosyl bromide (VIII),
m. 155.5-7.0° (decompn.)(CHCl3-petr. ether), [α]25 D 45° (c 1.2, CHCl3). Condensation of VIII with I in hot Me2CO gave
72% 2-[3,4,6-tri-O-acetyl-2-deoxy-2-(2,4-dinitroanilino)-β-D-glucopyranosyl]-2-thiopseudourea-HBr, m. 198-201°
(decompn.) (Me2CO-PrOH), [α]23 D -77° (c 0.5, MeOH). Condensation of VIII with II in Me2CO 1 hr. at room temp. gave
76% 3,4,6-tri-O-acetyl-1-S-acetyl-2-deoxy-2-(2,4-dinitroanilino)-1-thio-β-D-glucopyranose (IX), m. 163.5-4.0° (C6H6Et2O),
[α]22 D -29° (c 0.5, CHCl3). At longer reaction times an isomer of IX, m. 143-5°, [α]22 D -392° (c 0.27, CHCl3), was
isolated. Condensation of 3,4,6-tri-O-acetyl-2-amino-2-deoxy-α-D\-glucopyranosyl bromide-HBr (X) with I in boiling iso-
PrOH gave 61% 2-(3,4,6-tri-O-acetyl-2-amino-2-deoxy-β-D-glucopyranosyl)-2-thiopsendourea di-HBr, m. 179-81°
(decompn.) (iso-PrOH-EtOAc), [α]D -12° (c 1.06 MeOH). Condensation of X with III in dry Me2CO gave 72% 3,4,6-tri-O-
acetyl-2-amino-2-deoxy-β-D-glucopyranosyl ethylxanthate, isolated as the HCl salt (XI), m. 177-9° (decompn.) (EtOH-
Et2O), [α]20 D 23° (c 0.2, EtOH), pos. Cotton effect. Acetylation of XI gave VI. Simple O-Ac and S-Ac derivs. were prepd.
for infrared studies. Condensation of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide with II in Me2CO gave 88%
2,3,4,6-tetra-O-acetyl-1-S-acetyl-1-thio-β-D-glucopyranose, m. 119-20° (EtOH-Et2O), [α]25 D 10.5° (c 0.6, CHCl3).
Acetylation of 1-thio-DL-glycerol (XII) with Ac2O-NaOAc gave 83% 2,3-di-O-acetyl-1-S-acetyl-DL-glycerol, b0.01 120-40°,
n25 D 1.4701. Oxidn. of XII with H2O2 followed by acetylation with Ac2O-NaOAc gave 92% bis(2,3-diacetoxy-DL-propyl)
disulfide, b0.01 200-10°, n25 D 1.4883. Infrared spectra showed that OAc, SAc, and NHAc carbonyl absorptions could be
unambiguously differentiated in all compds. studied. An improved synthesis of IV was recorded.
~61 Citings
257. The synthesis and characterization of 4-0-(α,D-glucopyranosyl)-6-O-(β-D-glucopyranosyl)-D-glucose

By Goldstein, I. J.; Lindberg, Bengt
In an improvement over Klemer's synthesis of the title compd. (I) (CA 47, 10053i), 1,2,3,2',3',4',6'-hepta-Oacetyl-β-
maltose (II) (prepd. from hexa-O-acetyl-1,6-anhydro-β-maltose) (cf. CA 47, 9278f) (7.3 g.) and 5 g. Ag2O in 35 mL. dry
EtOH-free CHCl3 was shaken in the dark 1 h., 4.9 g. tetra-O-acetyl-α-D-glucopyranosyl bromide (III) and 0.5 g. I in 30
mL. same solvent added in 4 portions over 1 h., the mixt. shaken 72 h., filtered through Celite, the filtrate washed with dil.
Na2S2O3 and H2O, dried (Na2SO4), and the CHCl3 evapd. to give a sirup from which 0.85 g. II crystd. The remaining
sirup was deacetylated, diionized (Amberlite IR-120 and Dowex 3), and concd. to a sirup which was fractionated on a C-
Celite column (4 × 43 cm.) by elution with H2O then graded H2O-EtOH mixts. to give 1.8 g. D-glucose (IV), 2.6 g. maltose
(V), and 0.4 g. I [α]20 D 82°, contaminated with a trace of V. On electrophoresis in borate buffer V, gentiobiose (VI), and I
had MG of 0.36, 0.71, and 0.37. I was hydrolyzed in 0.33N H2SO4 to IV, V, and VI; hydrolysis with emulsin gave IV and V.
I (33 mg.) in 5 mL. H2O was treated with 20 mg. NaBH4, the mixt. allowed to stand overnight, deionized, H3BO3 removed
by distn. with MeOH, and the mixt. sepd. on paper to give 24 mg. of 4-0-(α-D-glucopyranosyl)-6-0-(β-D-glucopyranosyl)-
D-glucitol (VII) as a sirup, [α]20 D 53°. Partial acid hydrolysis of VII gave IV. VII (19 mg.) was treated with NaIO4 to
liberate 3.1 mol HCO2H and 0.95 mol CH2O. The remaining soln. was neutralized with BaCO3, filtered, the filtrate
treated with NaBH4, the mixt. worked up as above, hydrolyzed 1 h. with N H2SO4, neutralized (BaCO3), concd., extd. with
MeOH, and the ext. evapd. to a sirup of 2.1:1 glycerol-erythritol. Attempts to convert I to the bis(α-D-anomer) by
acetylation, refluxing the acetate with TiCl4, and deacetylation gave only unchanged I. The reaction of II and III with
quinoline as acid acceptor gave I as the only identifiable trisaccharide.
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258. Simultaneous determination of glycerol and fatty acids in glycerides by gas-liquid chromatography
By Horrocks, Lloyd A.; Cornwell, David G.
From Journal of Lipid Research (1962), 3, 165-9. Language: Unavailable, Database: CAPLUS
Glyceryl esters were subjected to hydrogenolysis with LiAlH4 and acetylated with Ac2O. Excess Ac2O was removed by
refluxing with EtOH. In this way, glycerides were converted to fatty alcohols and glyceryl acetates. Quant. acetylation
was demonstrated to be complete in 60 min. by thin-layer chromatography. Thus the acetates could be subjected to gas-
liquid chromatography and a simultaneous analysis of glycerol and fatty acid compn. obtained.
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259. Pleural and pericardial effusions associated with daily intravenous administration of acetylated tartaric acid
esters
By Hartwig, Quentin L.; Singleton, W. S.; Cotlar, Alvin M.
From Toxicology and Applied Pharmacology (1962), 4, 107-15. Language: Unavailable, Database: CAPLUS,
DOI:10.1016/0041-008X(62)90079-0
Diacetyltartaric acid esters of mixed mono- and diglycerides, used as one of the stabilizers of the intravenous fat
emulsion known as SR emulsion, was shown to produce pleural and pericardial effusions when given intravenously to
dogs.
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260. Lipogenesis and acetylation in animal tissues

By Gulyi, M. F.; Degtyar, R. G.; Kurskii, M. D.
From Tr. 2-oi[Vtoroi] Nauchn. Konf. po Vopr. Probl. Zhira v Pitanii, Leningrad (1962), 161-74. Language: Unavailable,
Database: CAPLUS
In in vivo and in vitro expts. acetate (I) had a ketogenic effect and stimulated synthesis of lipids in liver homogenates.
Fed to goats, I increased milk fat content. In in vitro expts. glycerol (II) stimulated formation of ketone bodies in the liver
of starving rabbits and increased formation of lipids in liver tissue of sated animals. Fed to goats, II increased milk fat
content and decreased the content of ketone bodies in the milk. α-Glycerophosphate behaved like I, but its effect was
more pronounced. EtOH is utilized better than I for lipid synthesis. Insulin had no effect on activation of I by liver
homogenates and a protein fraction contg. a I-activating enzyme, but increased the acetylation activity of liver
homogenates. Dialysis increased the acetylation capacity of homogenates, and suppressed the stimulating effect of
insulin. Insulin had no effect on the acetylation activity of a transacetylase-contg. protein fraction obtained from pigeon
liver. It is hypothesized that the activation of acetylation by insulin is due to fixing of some substance which inhibits this
process.
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261. Esterification of glycerol and polyglycerols with fatty acids. II. Optimum conditions of acetylation of
monoglyceridic emulsifiers with acetic anhydride
By Tomankova, I.; Pokorny, J.
From Sb. Vysoke Skoly. Chem.-Technol. Praze, Potravinarska Technol. (1962), 6(1), 243-9. Language: Unavailable,
Database: CAPLUS
cf. CA 60, 5758f. Complete (99%) acetylation is achieved only with a 450% excess of acetic anhydride for 30 min. The
fatty-acid compn. does not affect the rate of reaction. Quant. acetylation is best achieved at 138° (b.p. of the reaction
mixt.), not 100°; a suitable rate for continuous acetylation is achieved at 160° at moderately increased pressure, The
quant. reaction is complete in 10-15 min. Losses during isolation of the product increase with the hydroxyl value, degree
of unsatn. of the fatty acids, and concn. of AcOH in the aq. phase.
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262. Epoxy resins

By Blyakhman, E. M.
From Vestnik Tekhn. i Ekon.Inform. Nauchn.-Issled. Inst. Tekhn.-Ekon. Issled. Gos. Kom. Sov. Min. SSSR po Khim.
(1962), (4), 23-5. Language: Unavailable, Database: CAPLUS
Trimethylolethane(I), trimethylolpropane (II), glycerol, diethylene glycol, dimethyldimethylolmethane, and pentaerythritol
dichlorohydrin were used to obtain resins with an elevated heat capacity. Acetylation of resins based on I and II yielded
resins contg. ≤2%OH groups and having a high water resistance. The characteristics of the resins are given.
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263. Cellulose acetate filters

By Touey, George P.
CAPLUS
The title filters are improved by applying additive materials which are normally solid at room temp. but which are liquid at
temps, of 40-100° and miscible with plasticizers for cellulose acetate at 40-100° and which solidify with a particle size of
05-30µ. The additives are firmly bonded by the plasticizer to the cellulose acetate tow and form rods and ridges which
increase the smoke filtration efficiency of filters prepd. from the tow. The 3 groups of materials which are esp. suitable
are fatty acid esters, fatty acids, and fatty alcs. Preferred fatty acid esters are the monostearates of glycerol and
propylene glycol, the acetylated monoglycerides, and the hydrogenated castor oils. Suitable fatty acids have empirical
formulas CnH2nO2 and CnH2n-2xO2, where n is 10-24, and x is 01-5. Preferred fatty acids are myristic, palmitic. and
stearic since these acids are nontoxic and have little or no odor. Preferred fatty alcs. are stearyl alc. and cetyl alc. Thus,
a 5-ft. length of cellulose acetate low contg. 10,000 filaments of 8 denier/filament and having 9 crimps/in. was spread to a
width of 12 in. and sprayed on both sides with a soln. of 50:50 mixt. of glycerol monostearate (I) and glycerol triacetate
(II) at 70°. Analysis of the treated tow showed 64% cellulose acetate filaments, 18% I and 18% II. The treated tow was
pulled back into a compact bundle, fed into a cigaret-filter-plug making machine, wrapped in paper and cut into 90-mm
filter rods 25.5 mm. in circumference. After storage for 20 rain. at 28°, the rods were quite rigid. Microscopic examn. of
filaments from the open rods showed that substantially all of the filaments had a rough and irregular surface due to the
deposit of I which was firmly bound by plasticizer. Fifteenmin. tips were cut from the rods, attached to 85-mm. cigarets
which had been shortened by 15 mm. and the cigarets smoked for detn. of nicotine and tar content. As compared with
smoke of untipped 85-mm. cigarets, the smoke of cigarets tipped with the various filters contain the following amts. less
nicotine and less tar: Untreated cellulose acetate 11.8%, 13.8%; acetate filters contg. 18% II 10%, 10.4%; acetate filters
contg. 18% II and 18% I 35.8%, 31%; acetate filters eontg. 19% II and 19% stearic acid 34.5%, 37.5%; and acetate filters
contg. 16% II and 16% stearyl alc. 31%, 34%, resp.
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264. Antibiotic by culturing a new strain of Streptomyces

Fermentation is conducted with S. flavofungini in an aq. medium in aerobic conditions at a temp. of 26-9° and pH of 6-8.
The product is extd. with EtOAc. Extn. of the fermentation liquor may be effected after removing the mycelium and (or)
the solid phase contg. the mycelium may be extd. For the latter all aliphatic alc. may be used. The crude product is
recrystd. in a lower aliphatic alc. or EtOAc. The inoculum consists of 50 ml. beer yeast with 1 g. NaNO3, 0.5 g.
asparagine, 2.5 g. Na2HPO4, 0.25 g. KH2PO4, 0.25 g. KCl, and 0.25 g. MgSO4.7H2O in 400 ml. water with pH adjusted
to 7. It is sterilized and mixed with 25 ml. of a 40% soln. of glucose, sep. sterilized, so that the glucose content of the
nutrient is 2%. The resulting mixt. is made up to 500 ml. with sterilized water and inoculated with the organism grown on
a solid medium. Incubation is for 80 hrs. at 27° in a flask which is mech. agitated. This gives the preliminary inoculum.
The main inoculum is prepd. by adding to 4 1. tap water, 40 g. peptone, 16 g. glycerol, 2 g. MgSO4.7H2O, 20 g. KH2PO4,
resulting in 4.5 1. of nutrient whose pH is adjusted to 7.2. It is sterilized and 500 ml. of the preliminary inoculum is used
to inoculate it, followed by incubation at 25° for 36 hrs. with agitation. Fermentation is conducted at 27° with agitation at
240 r.p.m. and insufflation of sterile air through the broth at a rate of 0.5 vol. air/vol. of broth/min. To suppress froth
formation at the inception, 20 ml. sunflower oil is added and, at the end of fermentation, a further 20 ml. is added in small
proportions. After 48 hrs., the broth becomes brilliant yellow and thickens. After 36, 60, and 84 hrs. samples are
withdrawn for detn. of flavofungin and the content found to be, resp., 0.55, 1.25, and 1.55 g./l. Sterility of the broth is
checked each 12 hrs. In 84 hrs. the sugar content of the nutrient decreases to 0.2%; 70 1. of the broth contg. mycelium
is filtered, recovering 4 kg. of greenish yellow solids. This is refluxed with 4 1. EtOAc for 30 min. and the solvent sepd.
by filtration. This digestion is repeated 5 times with fresh 4-1. portions of EtOAc. The filtrates obtained are combined
and evapd. in vacuo at 40-50° until turbid; 5 1. of concentrate are obtained which, on cooling at ambient temp., yields
crystals of the antibiotic which are filtered off, washed with cold acetone, then with cold ether, and finally dried in vacuo.
The yield is 104 g. of yellow crystals. Evapn. of the mother liquor yields a further 6 g. of a product of similar purity. In
another example, flavofungin is catalytically hydrogenated in EtOH, using a C-Pd catalyst. Evapn. of the filtered liquor
vickls a vitreous product which is recrystd. from MeOH 3 times. The product consists of white needles with m.p. 149-51°.
The [αD in pyridine is between -5.6 and -9.1°. Its empirical formula on analysis is probably C30H58O10. In a further
example, flavofungin of m.p. 149-151° is acetylated in a mixt. of Ac2O and pyridine. The recrystd. product has m.p. of
141-2°, [α]d in pyridine -184°, and Ac content of 35% with an empirical formula C44H62O17, indicating the presence of 7
Ac groups and 7 OH groups. The acetylated product is insensitive to O. It can be deacetylated by treatment in an alc.
soln. of KOH to yield at product which has the same biol. and phys. properties as the original flavofnngiu.
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265. A-Nor steroids

By Camerino, Bruno; Valcavi, Umberto
A-Norandrostane derivs. were prepd. by base-catalyzed rearrangement of 4-hydroxytestosterone 17-acetate (I)
(Camerino, et al., CA 51, 1238c). I (8.9 g.) was refluxed 24 hrs. with 36 g. KOH in 360 ml. BuOH, 300 ml. H2O added,
and the mixt. evapd. to dryness under vacuum. The residue in 200 ml. MeOH was poured into 2800 ml. H2O and extd.
with 500 ml. CH2Cl2. The clarified and acidified aq. layer gave 5.3 g. crude A-norandrostane-3,17β-diol-3-carboxylic acid
(II), m. 243-45° (MeOH], [α]24 D 14° (c 1, dioxane). II (12 g.) in 600 ml. tetrahydrofuran was added over 30 min. to CH2N3
(from 25.2 g. nitrosomethylurea) in 300 ml. CH2Cl2 at 10-15° then stirred 1 hr. An excess of AcOH was added and after
30 min the org. layer was washed with 10% NaOH and H2O and evapd. under vacuum to give 11 g. II Me ester, m. 162-
5° (aq. MeOH), [α]24 D 19° (c 1, CHCl3). Me ester of II (3.8 g.) in 100 ml. tetrahydrofuran was added slowly to 2.5 g.
LiAlH4 in 380 ml. Et2O. The mixt. was boiled 30 min., cooled, 250 ml. H2O added, and acidified. The aq. layer was extd.
with EtOAc, the org. layers washed, dried, and evapd. under vacuum to give 2.8 g. 3-methylolA-norandrostane-3,17β-diol
(III), m. 200-5° (EtOAc), [α]24 D -10° (c 1, dioxane). III (2 g.) was shaken 5 hrs. at room temp. with 2.5 g. H5IO6 in 800 ml.
dioxane and 30 ml. H2O under CO2, then 1 hr. after the addn. of 0.9 ml glycerin. The filtrate was concd., H2O added,
and solid washed with aq. NaHCO3 to give 13 g. A-norandrostan-17β-ol-3-one (IV), m. 148-52° (aq. MeOH), [α]24 D -86°
(c 1, CHCl3). IV was also obtained by shaking 4 g. II with 40 g. NaBiO2 in 400 ml. HOAc and 100 ml. H2O 90 min. at
room temp., adding 800 ml. H2O and 100 ml. 15% NaOH, cooling, and extg. with C6H6. Evapn. gave 2.2 g. IV, m. 145-
50° (aq. MeOH). Acetylation of IV (overnight at room temp. gave IV 17-acetate, m. 167-70° (MeOH), [α]24 D -90° (c 1,
CHCl3). Oxidn. of IV with aq. CrO2-H2SO4 in Me2CO gave A-norandrostane-3,17-dione, m. 153-6° (MeOH).
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266. The synthesis of L-glycero-tetrulose 1-phosphate (L-erythrulose 1-phosphate)

By Gillett, J. W.; Ballou, Clinton E.
From Biochemistry (1963), 2(3), 547-52. Language: Unavailable, Database: CAPLUS, DOI:10.1021/bi00903a027
L-glycero-Tetrulose 1-phosphate ("L-erythrulose" 1-phosphate) has been prepd. by a series of reactions that parallel
those used previously for the syntheses of the D-isomer (Chu and Ballou, CA 55, 19802a). (-)-Inositol, prepared from
quebrachitol by demethylation with HI, was acetonated in acetone and ZnCl2 to give 1,2:5,6-di-O-isopropylidene-(-)-
inositol. After oxidn. with NaIO4 and redn. of the dialdehyde with NaBH4, the inositol derivative yielded 2,3:4,5-di-O-
isopropylidene-L-mannitol. Benzoylation then gave 1,6-di-O-benzoyl-2,3: 4,5-di-O-isopropylidene-L-mannitol. This
compd. was partially hydrolyzed and isomerized in an acidic aq. acetone mixt. to 3,4-isopropylidene-1,6-dibenzoyl-L-
mannitol, which, without isolation, was benzoylated to give 1,2,5,6-tetra-O-henzoyl-3,4-O-isopropylidene-L-mannitol. The
acetone group was removed by acid hydrolysis and 1,2,5,6-tetra-O-benzoyl-L-mannitol was obtained. The tetra-O-
benzoyl-L-mannitol was cleaved by oxidn. with lead tetroxide in glacial acetic acid, and the 2,3-dibenzoyl-L-
glyceraldehyde was oxidized to 2,3-di-O-benzoyl-L-glyceronic acid with peroxypropionic acid. The acid was converted to
2,3-dibenzoyl-L-glyceronyl chloride through the action of SOCl2, and then was condensed with CH2N2 at -50° to give 3,4-
di-O-henzoyl-1deoxy-1-diazo-L-glycero-tetrulose. Hydrolysis of the diazo ketone yielded 3,4-di-O-benzoyl-L-glycero-
tetrulose, which, on acetylation in dry methanol and HC(OMe)3 with H2SO4 as the catalyst, was converted to 3,4-di-O-
benzoyl-L-glycero-tetrulose di-Me acetal. Phosphorylation of this acetal with diphenylphosphorochloridate in pyridine
gave a sirup. By reductive removal of the phenyl groups and sapon. of the acyl substituents, L-glycero-tetrulose 1-
phosphate di-Me acetal was obtained and was isolated as the cryst. biscyclohexylammonium salt monohydrate. L-
glycero-Tetrulose 1-phosphate ("L-erythrulose" 1phosphate) was obtained from the acetal by mild acid hydrolysis. It was
reduced to L-threitol 1-phosphate by glycerol phosphate dehydrogenase and reduced nicotinamide-adenine-dinucleotide
at a rate about 1% of that found with dihydroxyacetone phosphate as the substrate. Rabbit muscle aldolase cleaved the
"L-erythrulose" 1-phosphate at a rate about 0.021 times that of D-fructose 1,6-diphosphate, and the equil. const. for the
reaction was 0.24 at pH 7.2.
~2 Citings
267. Synthesis of epoxide resins using polyhydric alcohols containing a quaternary carbon atom
By Blyakhman, E. M.
From Kakokrasochnye Materialy i ikh Primenenie (1963), (6), 7-10. Language: Unavailable, Database: CAPLUS
Glycidyl esters were prepd. from epichlorohydrin (I) and trimethylolethane (II), trimethylolpropane (III), 2,2-dimethyl-1-3-
propanediol, and pentaerythritol dichlorohydrin (IV) by adding dropwise over 3-4 hrs. a 50% NaOH soln. to the refluxing
soln. of I and polyhydric alc. The salt was filtered from the mixt., the I distd., and the remaining volatile material removed
at 120-30 and 10 mm. Dry, flaked caustic was also used and was added to vigorously stirred solns. of I (in 3-fold excess)
and polyhydric alc. at 50-60. In some cases, inert solvents were used. An acid catalyzed reaction was carried out in 2
stages, using 1 ml. concd. H2SO4 per OH in II, 0.75 ml. per OH in III, 0.50 ml. per OH in IV, 1.7 ml. per OH in glycerol
and 1.9 ml. per OH in pentaerythritol. Equiv. amts. of I and alc. were heated under reflux with H2SO4 until most of the I
reacted. The degree of reaction could be controlled by distg. I from the neutralized crude. The intermediate chlorohydrin
was dehydrohalogenated by heating with dry caustic to yield the resins. These aliphatic epoxides were acetylated with
Ac2O (1.5 moles/mole residual OH) at 70-5°. The product was extd. into PhMe and washed with 5% NaOH and then
with water. Thus, the OH content was reduced to <1%. The glycidyl esters could be esterified with stearic or oleic acids
(equiv. amt.) at 130 for 3 hrs. The reaction was quant. and gave oily liquids with oleic acid and considerable amts. of
low-melting solid with stearic acid. These materials were used as plasticizers and stabilizers for poly(vinyl chloride).
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268. Synthesis and proof of structure of tritiated glucose and its use in the study of the mechanism of UDPGal
(uridine diphosphogalactose)-C-4-epimerase
By Bevill, R. D.; Nordin, J. H.; Smith, F.; Kirkwood, S.
From Biochemical and Biophysical Research Communications (1963), 12(2), 152-6. Language: Unavailable, Database:
CAPLUS, DOI:10.1016/0006-291X(63)90253-5
Methyl 2,3,6-tri-O-Me-D-glucopyranoside was oxidized with CrO3 in pyridine to give the 4-oxo deriv. which was reduced
with NaBT4, and demethylated with BCl3, in methylene chloride. D-Glucose-4-T (I), isolated by paper chromatography,
was acetylated with acetic anhydride and NaOAc and the β-pentaacetate was converted in anhyd. H3PO4 to tritiated α-D-
glucose 1-phosphate (II). To det. the position of T, methyl α-D-glucopyranoside (III) was prepd. from I. III was treated
with HIO4 to yield HCOOH (IV) and D'-methoxy-D-hydroxymethyldiglycolaldehyde (V). IV was converted to its
ammonium salt and purified by sublimation. V was oxidized with Br2 in the presence of SrCO3 to yield Sr D'-methoxy-D-
hydroxymethyldiglycolate (VI). V was reduced with NaBH4 and hydrolyzed with HCl to yield glycerol (VII) and glycolic
aldehyde (VIII). VII was isolated as the tri-p-nitrobenzoate and VIII as the cryst. methone deriv. VI contained 40% of the
activity and positions 1 and 2 contained no activity. VI was hydrolyzed with HCl to give D-glyceric acid (IX) and glyoxylic
acid. IX, isolated by paper chromatography was treated with HIO4 to yield IV and formaldehyde (X). X was isolated as
the cryst. methone deriv. Tritiated D-glucose had 60% of the total activity in position 4 and 40% at position 6. Uridine
diphosphoglucose (UDPG) was obtained by mixing II, uridine triphosphate, tris(hydroxymethyl)aminomethane buffer,
MgCl2, C2H5SH, UDPG pyrophosphorylase, and cryst. inorg. pyrophosphatase. After 1 hr. at room temp. the mixt. was
adjusted to pH 8.7 and Saccharomyces fragilis UDPGal-C-4-epimerase was added. After 1-4 hrs. incubations HCl was
added and the nucleotide-bound sugars were hydrolyzed. T was retained by the hexose during epimerization at position
4. Possibility of stereospecific removal of an hydroxyl group and its reintroduction is not ruled out.
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269. Stable sudanophilia. Histochemistry of the Sudan dyes

By Terner, Jacob Y.; Schnur, James; Gurland, Judith
From Laboratory Investigation (1963), 12, 405-14. Language: Unavailable, Database: CAPLUS
Histochem. blocking reactions (methylation and deamination) and enzyme inhibitors (CN- and F-) were utilized to
demonstrate the dependence of solvent-resistant Sudan dye staining of paraffin sections upon tissue acid groups, and of
polymorphonuclear leukocytes upon a peroxidase type of enzyme reaction. Methylation-labile solvent-resistant Sudan
Black B staining at pH 2.0 of structures stained also by Oil Red O or acetylated Sudan Black B in hydrated, glycerol-
mounted prepns. were proposed as criteria for acid lipids in paraffin section. Stable sudanophilia was defined as any
staining obtained with Sudan-type dyes which resists solvent extn. applied for times and temp. used in routine
dehydration and permanent mounting of tissues. Polymorphonuclear granule sudanophilia is an enzymically dependent
process related to, and perhaps equivalent to, peroxidase activity. Lipid peroxides of the cell may be the substrates for
the reaction in the absence of an exogenous source of peroxide. These will decomp. naturally, forming alcs. or ketones,
and hence in the absence of exogenous peroxides, the sudanophilic reaction is somewhat diminished after slides have
aged for 48 hrs., and it is absent after 10 days. Sudanophilia and the benzidine reaction are still evident after 10 days in
the presence of H2O2. The requirement of supersatd. solns. of Sudan dyes for optimal reactions, and the strong
reactions given by predicted side products of the synthesis of Sudan Black B, suggest that the major component of
various com. Sudan prepns. used is not necessarily the substrate for peroxidase reaction. Oxidn. of side products of
Sudan synthesis renders them less sol. in org. solvents than is the ordinary Sudan stain. Polymorphonuclear leukocyte
granules do not stain with Sudan dyes after extn. with org. solvents; this was interpreted as evidence for their lipid nature
and the concept that the Sudan dyes dissolve in this lipid. However, extn. with org. solvents at higher temp. irreversibly
inhibits both the sudanophilic and classic peroxidase reactions, and may be attributed to a loss of the enzyme itself rather
than to loss of cell lipids. These extns. destroy the integrity of the granule membranes and allow the enzyme to escape.
~1 Citing
270. Reactions of carbohydrate derivatives during gas-liquid chromatography

By Bishop, C. T.; Cooper, F. P.; Murray, R. K.
From Canadian Journal of Chemistry (1963), 41(9), 2245-50. Language: Unavailable, Database: CAPLUS,
DOI:10.1139/v63-326
The following reactions have been shown to occur during gas-liquid chromatography of carbohydrate derivatives: (a)
deamidation, (b) change in size of the sugar ring, (c) rearrangement of acetal groups, (d) degradative rearrangement of
acetylated amino sugars. The results emphasize that stability of a compd. under conditions used in gas-liquid
chromatography is a necessary prerequisite to the application of that technique; the precautions that should be followed
to det. stability are indicated.
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271. Preparation of the threo- and erythro-forms of DL-guaiacylglycerol and of DL-veratrylglycerol

By Adler, Erich; Gustafsson, Bo
From Acta Chemica Scandinavica (1963), 17, 27-36. Language: German, Database: CAPLUS
cf. CA 48, 5147g. Hydrogenation of 3,4-dimethoxyphenylpropiolic acid in EtOH with Lindlar catalyst 50 min. gave 70%
cis-methylferulic acid (I), m. 104°, which with CH2N2 yielded 90% Me ester, prisms, m. 92-3°. Redn. of 30 g. Me trans-
methylferulate (II) in 200 cc. dioxane with 5.7 g. LiAlH4 in 500 cc. abs. Et2O, addn. of H2O and dil. H2SO4, extn. with
CHCl8, and distn. of the residue of the CHCl3 ext. gave 70% methylconiferyl alc., b5 110-20°, needles, m. 79-80°; Ac
deriv. (III) b12 190-5°. Treating 80 mg. III in 3 cc. Et2O-C5H5N (25:1) 16 hrs. with O.1 g. OsO4 in 2 cc. Et2O and
hydrolyzing the osmic ester in 2 cc. EtOH with 0.65 g. Na2SO3 in 3 cc. H2O 1 hr. at 100°, evapg. the filtered soln. in
vacuo, and extg. the residue with CHCl3 gave 85% DL-threoveratrylglycerol (IV), m. 109-10°. Treating II similarly with
OsO4 and acetylating the hydrolyzed Os ester gave 60% DL-threo-α,β-diacetoxymethylhydroferulic acid (V), prisms, m.
148-9°. Esterification of V with CH2N2 followed by redn. yielded IV. Refluxing 15 g. Me α-bromo-β-acetoxymethyl-
hydroferulate in 65 cc. AcOH and 65 cc. Ac2O 45 min. with 7 g. AgOAc, treating the filtered soln. with H2O, evapg. the
soln. in vacuo, extg. the residue with CHCl3, evapg. the washed (NaHCO3) soln., and crystg. the residue from Et2O-
C6H14 gave 41% Me threo-α,β-diacetoxymethylhydroferulate (VI), m. 102-3°. Concn. of the mother liquor gave 40%
erythro isomer (VII), prisms, m. 71-3°. VI was also obtained in 10% yield when 4.44 g. II was oxidized with KMnO4 at -
50° according to Riiber (CA 9, 2244). Redn. of VII with LiAlH4 gave DL-erythroveratrylglycerol (VIII), plates, m. 92-3°,
λmax. 278 mµ (log ε 3.52). The infrared spectra of IV and VIII differed distinctly. When Me erythro-
diacetoxyacetylhydroferulate was reduced with LiAlH4 (cf. loc. cit.) and the acid step was avoided by neutralizing the
reaction mixt. with AcOH, 55% DL-erythro-guaiacylglycerol (IX), m. 83-4° was obtained; IX tetraacetate m. 86-8°. IX and
CH2N2 gave 90% VIII. Treating 0.31 g. IX with 0.1N H2SO4 neutralizing the mixt. with BaCO8, evapg. the filtered soln. in
vacuo, and treating the residue with moist EtOAc gave 0.18 g. unchanged IX and, from the mother liquor, 0.05 g. threo-
DL-guaiacylglycerol (X); tetraacetate m. 113-14°. Benzyl-coniferyl alc. benzoate (0.515 g.) (Freudenberg and Achtzehn,
CA 50, 1661h) was treated in 12 cc. Et2O-C5H5N with 0.35 g. OsO4 and the ppt. formed was boiled 1 hr. with 2.3 g.
Na2SO3 in 10 cc. H2O, giving threo-(O-benzylguaiacyl)glycerol, m. 101°, which when treated in EtOH with
prehydrogenated PdCl2-BaSO4, yielded X as a sirup; tetraacetate, 70%, m. 113-14°. X and CH2N2 gave 70% IV.
Careful fractionation of the mother liquor of the Me erythro-α,β-diacetoxyacetylhydroferulate gave 10% threo isomer,
prisms, m. 81-2°, which with LiAlH4 gave 55% X. Treating 0.074 g. trans-methylisoeugenol (XI) with OsO4 gave 75% DL-
threo-methylisoeugenol glycol, m. 90°, which was also obtained in 15% yield when 1.93 g. XI was treated at -50° with
1.96 g. KMnO4. Acetylation of 3.3 g. XI in 3 cc. AcOH with 6.6 g. Pb(OAc)4 and redn. of the α,β-
diacetoxyveratrylpropane formed with LiAlH4 gave 2 g. of a product, m. 80-100°, which on fractional crystn. yielded
crythro-methylisoeugenol glycol, m. 123°, and the threo isomer, m. 88°.
~7 Citings
272. Paper chromatographic analysis of explosives

By Krien, Gottfried
From Explosivstoffe (1963), 11(10), 207-9. Language: Unavailable, Database: CAPLUS
Glycerol trinitrate (I), ethylene glycol dinitrate (II), 2,4,6-trinitrotoluene (III), 2,4-dinitrotoluene (IV),
trinitrophenylmethylnitramine (V), and pentaerythritol tetranitrate (VI) are sepd. from each other and identified by
chromatography. All the components can be sepd. in 1 developing process. Completely acetylated (40-5% Ac) filter
paper was used for the invert-phase chromatography with Partridge soln. (BuOH 4, AcOH 1, and H2O 1 part by vol.) as
the liquid phase. The samples were dissolved in C6H6 or PbCl to form a 1% soln. and 0.005-0.02 ml. of the soln. was
applied to the acetylated paper. After 2.5-4 hrs., the solvent was evapd. and the chromatogram was developed with the
BuOH-AcOH soln. at 20°. The temp. was raised to 40° and dark spots under ultraviolet light showed the presence of III,
IV, and V. The spots of the nitrate explosives could be made visible by treatment with diphenylamine-H2SO4 or by
conversion to azo dyes. Identification was made by Rf values and by comparison with known substances. The method
is esp. suitable for identifying polyalc. nitrates whose compn. is important for safety evaluations in view of the
congealability of nitroglycerin.
~0 Citings
273. Orcein pigments. XX. The autoxidation products of 2,5-dimethylresorcinol in ammonia and potassium
hydroxide
By Musso, Hans; Zahorszky, Uwe I.
The autoxidn. of 2,5,1,3-Me2(HO)2C6H2 (I) in NH4OH yielded dyes analogous to those obtained from 3,5-(HO)2C6H3Me
(II). The autoxidn. in aq. KOH yielded, in addn. to the dimeric mono- and diquinone, a trimeric diquinone which could not
be identified with certainty in the product from II. The autoxidn. of I proceeds faster and furnishes better yields of the
higher oxidized products which are more stable than those from II. I (14 g.) in 140 cc. concd. NH4OH kept 25 days at
room temp. in air while being treated daily with dry NH3 during a few min., concd. in vacuo over concd. H2SO4, and dried
over P2O5 yielded 16.8 g. crude, violet-black, amorphous powdery xylorcein which, extd. at about 70° with the upper
phase of 5:1:2.6:5 C6H6-BuOH-AcOH-H2O and then chromatographed on cellulose powder, yielded 0.46 g. III (R = OH)
(IV), red-brown crystals, m. 340° (decompn.) (MeOH-CHCl3), 0.85 g. (crude) trans-V (R = OH) (VI) (the OH groups on the
benzene rings are in the trans configuration with respect to the phenoxazone plane), red-brown crystals, m. 280° (MeOH-
CHCl3), 0.94 g. (crude) cis-V (R = OH) (VIA), red-brown crystals, m. 280° (decompn.), 0.35 g. (crude) III (R = NH2) (VII),
red rodlets, m. 370° (decompn.) (MeOH-CHCl3), 0.90 g. (crude) trans-VIII (R = O) (IX) rodlets with a green-black luster,
m. 300° (decompn.), 1.30 g. (crude) cis-VIII (R = O), (IXA), green-black glistening rodlets, m. 350° (decompn.), 0.26 g.
trans-X (XI), green-black glistening crystals, m. 350° (decompn.) (MeOH-CHCl3), 0.38 g. (crude) cis-X, green-black
needles, m. 350° (decompn.) (MeOH-CHCl3), 0.35 g. (crude) cis-VIII (R = NH) (XII), and 0.25 g. (crude) trans-VIII (R =
NH) (XIIA). IV (50 mg.) in 5 cc. dry C5H5N treated at room temp. with 5 cc. Ac2O, evapd. after 24 hrs., and the residue
chromatographed on silica gel yielded 26 mg. red triacetate B of IV, m. 222-5° (decompn.) (C6H6-cyclohexane), and 7
mg. triacetate A of IV, yellow needles, m. 234-7° (decompn.). VI (100 mg.) gave similarly 15.9 mg. orange triacetate of
VI, m. 240° (decompn.) (C6H6-cyclohexane). VI (52 mg.) in 20 cc. EtOH warmed 5 hrs. on the water bath with 250 mg.
o-C6H4(NH2)2 (XIII) in 10 cc. AcOH and evapd., and the residue evapd. with C5H5N and chromatographed on silica gel
yielded 20 mg. phenazine deriv. of VI, orange crystals, m. 231-3° (decompn.) (C6H6-cyclohexane). VIA (43 mg.) treated
24 hrs. with Ac2O-C5H5N at room temp. and evapd., and the residue chromatographed on CaSO4 yielded 21 mg.
triacetate of VIA, orange-yellow crystals, m. 239-42° (decompn.). VIA (77 mg.) and XIII yielded 16.5 mg. yellow
phenazine deriv., m. 213-17° (decompn.) (C6H6-cyclohexane). VII (120 mg.), Ac2O, and NaOAc refluxed 20 min., and
the crude product chromatographed successively on silica gel and CaSO4 yielded 10.5 mg. red triacetate of VII, m. 160-
3° (decompn.). IX (139 mg.) acetylated and chromatographed on silica gel gave 34 mg. N-Ac tetraacetate deriv. of IX,
red rodlets, m. 165-70° (decompn.). IXA (96 mg.) acetylated with Ac2O-NaOAc and chromatographed on CaSO4 yielded
21 mg. N-Ac tetraacetate deriv. of IXA, orange-red crystals, m. 172-5° (decompn.). XI (30 mg.) with C5H5N-Ac2O yielded
during 3 days at room temp. 13 mg. N-Ac triacetate deriv. of XI, orange crystals, m. 164-7° (decompn.) (C6H6-
cyclohexane), cis-X (55 mg.) yielded similarly 13.9 mg. N-Ac triacetate deriv. of cis-X, red-orange crystals, m. 172-5°
(decompn.) (C6H6-cyclohexane). Crude XII (160 mg.) or 120 mg. XIIA were repptd. from a few cc. MeOH with C6H6 and
filtered, and the blue amorphous residues, which did not melt up to 340° but decompd. with effervescence when inserted
at 240°, were isolated as XII.1/2H2SO4 and XIIA.1/2H2SO4.MeOH, resp. Pure VI or VIA (1 mg.), each in 1 cc. glycerol
heated in vacuo in a sealed tube at 185° and partitioned after 1 hr. between BuOH-H2O, and the residues from the red
BuOH phases chromatographed on cellulose powder showed that both dyes were isomerized to about 50%. IX and IXA
heated to 200° during 1 hr. turned red-brown; in glycerol during 1.5 hrs. at 200° only brown-black decompn. products
were formed. I (10 g.) and 8.6 g. KOH in 200 cc. H2O kept 5 days at room temp. in the air, acidified with dil. H2SO4, and
extd. with BuOH yielded 8.6 g. dark brown mass which dissolved in 100 cc. upper phase of BuOH-0.2M phosphate buffer
(pH 7) and chromatographed on cellulose powder yielded 2.2 g. 6-hydroxy-2,5-dimethyl-3-(4,6-dihydroxy-2,5-
dimethylphenyl)-1,4-benzoquinone (XIV), red rodlets, m. 223-4° (MeOH CHCl3), 60 mg. 2,5-dimethyl-4,6-bis(4-hydroxy-
3,6-dioxo-2,5-dimethyl-1,4-cyclohexadienyl)resorcinol (XV), orange rodlets, m. 282-3° (MeOH), pK 6.80, and 752 mg.
4,4'-dihydroxy-3,6,3'6'-tetramethylbiphenyl-2,5,2',5'-diquinone (XVI), orange-yellow rhombs, m. 208-10° (MeOH and
sublimed in vacuo at 170°). XIV (195 mg.) in 5 cc. C5H5N and 5 cc. Ac2O evapd. after 0.5 hr. and chromatographed on
silica gel yielded 197 mg. triacetate of XIV, yellow crystals, m. 156-7° (C6H6-cyclohexane). XIV (245 mg.), 5 cc. Ac2O,
and a little NaOAc refluxed 5 min. while being treated with Zn dust in small portions and evapd. yielded 380 mg.
3,4,6,4',6'-pentaacetoxy-2,5,2',5'-tetramethylbiphenyl, m. 182-3° (C6H6-cyclohexane). XIV (175 mg.) and 200 mg. XIII in
4 cc. AcOH heated 0.5 hr. on the water bath and evapd., and the residue chromatographed on silica gel yielded 150 mg.
phenazine deriv. (XVII), yellow-green crystals, m. 259-60° (EtOH-C6H6). XVII (120 mg.) acetylated with 5 cc. C5H5N and
5 cc. Ac2O, and the product chromatographed on silica gel yielded 118 mg. triacetate of XVII, yellow-brown crystals, m.
200-2° (EtOH). XV (14.4 mg.) in 5 cc. Ac2O refluxed 5 min. with a small amt. NaOAc while being treated with Zn dust in
small portions, and the product chromatographed on silica gel gave 13.2 mg. 3,5-diacetoxy-2,6-bis(3,4,6-triacetoxy-2,5-
dimethylphenyl)-p-xylene, m. 204-5° (C6H6-cyclohexane). XVI (113 mg.) yielded similarly 109 mg. yellow diacetate of
XVI, m. 142-3° (C6H6-cyclohexane). XVI (86 mg.) acetylated reductively yielded 126 mg. [2,5,3,4,6-Me2(AcO)3C6]2, m.
188-90° (C6H6-cyclohexane). XVI (47 mg.) and 150 mg. XIII in 5 cc. AcOH heated 0.5 hr. on the water bath, and the
product chromatographed on silica gel yielded 20 mg. phenazine deriv. (XVIII), black-blue needles, m. 229-31° (EtOH).
XVIII (200 mg.) in 3 cc. C5H5N treated with 5 cc. Ac2O and evapd. immediately in vacuo and the residue
chromatographed on silica gel yielded 94 mg. 3,3'-diacetoxy-1,4,1',4'-tetramethyl-2,2'-biphenazine, pale yellow, m. 299-
300° (C6H6-cyclohexane). The infrared absorption max. of the various compds. described and the ultraviolet absorption
max. of the various quinone are tabulated.
~2 Citings
274. Modes of formation of 2-isocyanato-4,5-dimethylphenoxazone

By Musso, Hans
From Chemische Berichte (1963), 96(7), 1945-7. Language: Unavailable, Database: CAPLUS
The title compd. (I) is formed as a by-product in the acetylation of 3-amino-4,5-dimethyl-2-phenoxazone (II) with Ac2O-
NaOAc. The formation of the I is explained by the elimination of Me2CO from the 3-AcCH2CONH analog (III) of I. 2,3-
H2N(HO)C6H3Me (1.40 g.) in 20 cc. EtOH treated with 10 g. K3Fe(CN)6 in 70 cc. 2N NaOAc gave 953 mg. II, brown-
violet needles, m. 233° (C6H6). II (300 mg.), 100 mg. NaOAc, and 20 cc. Ac2O refluxed 15 min. and evapd., and the
residue chromatographed on silica gel gave 5.4 mg. I, orange needles, deeompd. 2205° (slow heating), 227-30° (rapid
heating), 8.5% unchanged II, and 79.9 mg. 3-AcNH analog (IV) of II, orange needles, m. 25860° (decompn.)(sublimed in
vacuo at 140°), and finally 162 mg. 3-Ac2N analog (V) of II, orange rodlets, m. 205-7° (decompn.) (sublimed in vacuo at
120°). II (120 mg.) in 50 cc. refluxing xylene treated 10 min. with COCl2, blown with N, and evapd., and the residue
chromatographed on silica gel gave 90.8 mg. I. III (17 mg.), 5 cc. Ac2O, and 10 cc. NaOAc refluxed 15 min. and evapd.
gave 1.8 mg. I. A similar run with 40 mg. III during 0.5 reflux time gave only 2.3 g. I, m. 217-19°, 4.5 mg. IV, and 6.2 mg.
~1 Citing
275. Derivatives of corticosteroid side-chain condensations. V. Preparation of 21-monoacetates of 17α,20β-,21-

triols. New examples for the alkyl migration in glycerol side chains
By Gardi, Rinaldo; Vitali, Romano; Ercoli, Alberto
From Gazzetta Chimica Italiana (1963), 93(12), 1642-59. Language: Unavailable, Database: CAPLUS
cf. CA 59, 2898e, 6474e. Corticosteroids with dihydroxyacetone side chains were converted with aliphatic and
cycloaliphatic ketone enol ethers into mixed 21-alkyl acetals; these yielded, by successive selective redn. of the 20-oxo
group, acetylation, and hydrolysis under mild conditions, the 20-acetates of the corresponding 17α,20β,21-triols, which,
in the presence of acids or bases, were rearranged to the 21-monoacetates. It was demonstrated indirectly that the 20
→ 21-acyl migration of the 17α,20β,21-triols, previously observed to occur by the action of acids, proceeds also in basic
medium. Prednisolone (I) (3 g.) and 30 mg. C5H5N.p-MeC6H4SO3H in 10 cc. dry dioxane stirred about 15 min. with 3 cc.
EtCOMe enol Me ether (II) yielded 1.5 g. III (R = α-H, β-OH) (IV), m. 204-5° (Et2O), [α]D 98° (all in 0.5% dioxane at 24 ±
1°). Similarly was prepd. III (R = O), m. 217-19°, [α]D 157°. I (5 g.) in 15 cc. tert-BuOH contg. 50 mg. C5H5N.p-
MeC6H4SO3H treated 0.5 hr. with 5 cc. II gave 4.35 g. 21-EtMe(MeO)C ether (V) of I, m. 186-7° (Et2O-MeOH), [α]D
87.5°. Similarly was prepd. the 21-Me2(MeO)C ether (VI) of I, m. 178-9°, [α]D 89°. I (5 g.) and 50 mg. C5H5N.p-
MeC6H4SO3H in 1 l. CH2Cl2 refluxed 0.5 hr. with 10 cc. cyclohexanone enol Me ether (VII) gave 2.1 g. 21-(1-
methoxycyclohexyl) ether (VIII) of I, m. 201-3° (CH2Cl2-MeOH), [α]D 86°. Similarly were prepd. the 21-(1-
methoxycyclopentyl ether) of I, m. 188-90°, [α]D 88°, and the 21-(1-methoxycyclohexyl) ether of prednisone (IX), m. 113-
15°, [α]D 139°. V (4 g.) in 20 cc. dry C5H5N treated with 4 g. CrO3 in 40 cc. C5H5N yielded 2.17 g. 21-EtMe(MeO)C ether
(X) of IX, m. 159-61° (Et2O-MeOH), [α]D 143° V (1.5 g.) in 60 cc. HCONMe2 treated 18 hrs. at room temp. with 300 mg.
NaBH4 in 10 cc. H2O gave 750 mg. 21-EtMe(MeO)C ether of 1,4-pregnadiene-11β,17α,2Oβ,21-tetrol-3-one (XII), m. 202-
3o (MeOH), [α]D 25°. XI (2 g.) with 20 cc. C5H5N and 10 cc. Ac2O gave 800 mg. 20-acetate (XIII) of XI, m. 208-10°
(Et2OMeOH), [α]D 62°. VIII (1 g.) in 40 cc. HCONMe2 reduced with NaBH4 yielded 410 mg. 20β-OH analog, m. 136-9°,
which acetylated gave 230 mg. 20-acetate 21-(1-methoxycyclohexyl) ether (XIV) of XII, m. 207-9° (CH2Cl2MeOH), [α]D
61.8°. XIII (200 mg.) in 2 cc. tetrahydrofuran (THF) treated 10 min. with 0.1 cc. 2N (CO2H)2 gave 125 mg. 20-acetate
(XV) of XII, m. 225-6° (MeOH), [α]D 89°. XIV (280 mg.) gave similarly 163 mg. XV, m. 220-5°, [α]D 89°. XV (50 mg.) in 1
cc. C5H5N treated with 0.5 cc. Ac2O gave 30 mg. 20,21-diacetate (XVI) of XII, m. 250-2° (MeOH), [α]D 110°. X (2.5 g.) in
100 cc. HCONMe2 treated 40 min. with 500 mg. NaBH4 in 20 cc. H2O, and the oily product (1.6 g.) treated with 15 cc.
C5H5N and 7.5 cc. Ac2O and then heated 5 min. at 40-50° in 10 cc. THF with 2 cc. 2N (CO2H)2 yielded 300 mg. 20-
acetate (XVII) of 1,4-pregnadiene-17α,20β,21-triol-3,11-dione (XVIII), m. 192-5° (MeOH-Et2O), [α]D 147°. XVII (25 mg.)
acetylated gave the 20,21-diacetate of XVIII, m. 235-7°. XVII (30 mg.) in 50 cc. dry C6H6 refluxed 15 min. with 1 g. p-
MeC6H4SO3H yielded the 21-acetate (XIX) of XVIII, m. 220-5° (Me2CO-MeOH). XVII (30 mg.) in 1 cc. THF and 0.2 cc.
H2O treated with 0.04 cc. Et3N during 45 min. at room temp. gave 23 mg. XIX, m. 220-5° (Me2CO-MeOH), [α]D 118°. XV
(300 mg.) in 8 cc. THF and 1.6 cc. H2O treated 45 min. with 0.3 cc. Et3N yielded 200 mg. 21-acetate of XII, m. 215-17°
(MeOH), [α]D 40.5°, which acetylated gave XVI. Acetate (5 g.) of I in 200 cc. HCONMe2 treated 15 hrs. at 20-5° with 1 g.
NaBH4 in 40 cc. H2O yielded 3.1 g. 21-acetate of XII, m. 215-17° (Me2CO), [α]D 40°. 21-Acetate (XX) (1 g.) of 1,4-
pregnadiene-17α,20α,21-triol-3,11-dione (XXI) with BzCl in C5H5N gave the 20-benzoate (XXII), m. 241-3° (CH2Cl2-
MeOH), [α]D 43°. XXII (5 mg.) in 1 cc. MeOH treated with 0.05 cc. 0.05, 0.1, and 1% KOH-MeOH and chromatographed
on paper demonstrated the formation of the 21-benzoate of XXI. XXII (0.5 g.) and 0.4 g. p-MeC6H4SO3H in 20 cc. AcOH
and 4 cc. Ac2O kept overnight under N yielded 80 mg. 20-benzoate 17,21-diacetate (XXIII) of XXI, m. 214-17° (MeOH),
[α]D 7.8°. XXIII (5 mg.) in 1 cc. MeOH treated 20 hrs. with 0.01 cc. 1% KOH-MeOH and chromatographed on paper gave
a mixt. of the 20,21-diester, XII, and the 21-monobenzoate of XII. 20,21-Diacetate (2 g.) of XXI acetylated gave 830 mg.
triacetate of XXI, m. 213-15° (MeOH), [α]D 17.5°; a sample hydrolyzed with 1% KOH-MeOH gave after 30 min. the 20,21-
diacetate and then the triol XXI. 4-Pregnene-17α,20α,21-triol-3,11-dione (XXIV) (2.5 g.) in 15 cc. HCONMe2 treated
overnight at 0-5° with 7.5 g. ClCH2CO2H and 5 g. (ClCH2CO)2O yielded 2 g. 21-chloroacetate (XXV) of XXIV, m. 238-41°
(MeOH). XVIII (1.4 g.) gave similarly 1.3 g. 21-chloroacetate of XVIII, m. 187-90° (Et2O-MeOH), [α]D 117.5°. XXV (1.5
g.) in 7.5 cc. HCONMe2 and 7.5 cc. Ac2O heated overnight on a water bath gave 900 mg. 20-acetate (XXVI) of XXV, m.
248-50° (MeOH-Me2CO), [α]D 89°. 21-Chloroacetate (1 g.) of XVIII gave similarly 300 mg. 20-acetate 21-chloroacetate
of XVIII, m. 206-8° (MeOH), [α]D 165°. XXVI (380 mg.) in 3.5 cc. dry dioxane treated with 10 cc. 4% Me3N in dioxane
gave 413 mg. XXVII (20α), m. 185-8° (decompn.). Similarly was prepd. the 1,4-pregnadiene analog (XXVIII) of XXVII, m.
193-5° (decompn.). XXVII (250 mg.) in 3 cc. H2O treated 30 sec. with 0.24 cc. 2N NaOH yielded 150 mg. 21-acetate of
XXV, m. 248-50° (CH2Cl2-MeOH). XXVIII (300 mg.) in 5 cc. H2O treated with 0.285 cc. 2N NaOH yielded 154 mg. 21-
acetate of XVIII, m. 221-6° (MeOH).
~0 Citings
276. Verrucarin and roridin. IV. Structure of verrucarol and roridin C

By Gutzwiller, J.; Mauli, R.; Sigg, H. P.; Tamm, Ch.
From Helvetica Chimica Acta (1964), 47(8), 2234-62. Language: German, Database: CAPLUS,
DOI:10.1002/hlca.19640470817
cf. CA 59, 8795a. Verrucarol (I), the sesquiterpenoid moiety of the verrucarins and roridins, has been correlated with
trichodermin (II) and with trichothecolon. On the basis of further degradation to known fragments, I is assigned the
represented structure. Roridin C (III) is shown to be identical with trichodermol (IIIa), the hydrolysis product of II. Thus,
5.73 g. verrucarin A (contg. traces of verrucarin B) in 750 ml. MeOH was stirred with 60 g. K2CO3 in 200 ml. H2O 5 hrs.
at 20° to obtain 2.69 g. I, m. 155-6° (Me2CO-Et2O), [α]22 D -39 ± 2° (c 1.069, CHCl3); di-O-Ac deriv. (IV) m. 148-50°
(Me2CO-Et2O-petr. ether), [α]25 D -17 ± 1° (c 1.221, CHCl3); di-O-Bz deriv. m. 151-2° (Et2O-petr. ether), [α]29 D -64 ± 2°
(c 1.130, Me2CO). I (1.48 g.) in 10 ml. abs. tetrahydrofuran (THF) and 200 ml. Et2O was added in portions to a stirred
suspension of 1.5 g. LiAlH4 in 100 ml. Et2O at 0° and the mixt. refluxed 4 hrs. to obtain 1.21 g. dihydroverrucarol B (V),
m. 100-18° (Me2CO-Et2O). V prepd. by LiAlH4 cleavage of the di-O-acetyldihydro deriv. (VI) of I showed a double m.p. at
103-5° and 116-18° (Me2CO-Et2O), [α]29 D -35 ± 2° (c 0.990, CHCl3). Acetylation of V with Ac2O in pyridine gave VI, m.
142-4° (Et2O), [α]29 D -1 ± 1° (c 0.991, CHCl3), the di-O-acetyldeoxy deriv. of I, and IV. I (65 mg.) in 15 ml. Me2CO was
oxidized with CrO3 reagent (Helferich, CA 15, 2081) to give 34 mg. the oxo aldehyde (VII), m. 163-5°; [α]23 D -4 ± 1° (c
0.975, CHCl3). Oxidn. of V with CrO3 in Me2CO gave VIII, m. 172-5° (Me2CO-Et2O-petr. ether), [α]23 D -26 ± 1° (c 1.085,
CHCl3). Hydrogenation of 213 mg. I in AcOEt with H on 50 mg. Pd-C under normal conditions 16 hrs. (1 equiv. H was
consumed) gave 184 mg. dihydroverrucarol A (IX), m. 149-51° (Me2CO-Et2O-petr. ether), [α]26 D -6 ± 1° (c 1.101,
CHCl3); di-O-Ac deriv. m. 97-100° (Et2O-petr. ether), [α]24 D -13 ± 2° (c 0.62, CHCl3). Treatment of 150 mg. IX in Et2O-
THF with 100 mg. LiAlH4 gave 111 mg. tetrahydro deriv. (X) of I, m. 164-6° (Et2O), [α]24 D -9 ± 1° (c 1.097, CHCl3); di-O-
Ac deriv. prepd. Oxidn. of 90 mg. IX with 0.2 ml. CrO3 in Me2CO gave 40 mg. XI, m. 115-17° [α]23 D 55 ± 2° (c 0.87,
CHCl3). Similarly was prepd. XII, m. 116-18° (Et2O-petr. ether), [α]23 D 52 ± 2° (c 0.85, CHCl3), from X. To 1.05 g. I in
10 ml. abs. pyridine was added 1.5 ml. MeSO2Cl in 3 portions (each after 2 hrs.) and the mixt. kept 24 hrs. at 25° to give
1.62 g. di-O-mesylverrucarol (XIII), m. 184-5° (CH2Cl2-Et2O), [α]21 D -9° (c 0.98, CHCl3). XIII (1.19 g.) and 3 g. NaI in 50
ml. Me2CO was heated 24 hrs. at 100° in an autoclave to give 939 mg. XIIIa (R = CH2OSO2Me, R1 = OSO2Me) (XIV), m.
155-6°. Refluxing 101 mg. XIV in 2 ml. 95% EtOH with 300 mg. Zn powder 2 hrs. gave 25 mg. XIIIa (R = Me, R1 =
OSO2Me) (XV), m. 168-70° (Et2O-pentane), [α]21 D -22° (c 0.56, CHCl3). Treatment of 110 mg. IIIa in 1 ml. abs. pyridine
with 0.5 ml. MeSO2Cl first at 0°, then 3 hrs. at 20°, gave 42 mg. monomesyltrichodermol (XVa), m. 167-8°, [α]21 D -24° (c
0.85, CHCl3). Analogously was prepd. monomesylroridin (XVb), m. 167-8°, [α]25 D -29 ± 2° (c 0.735, CHCl3). XV, XVa
and XVb are identical. A soln. of 384 mg. XV in 40 ml. abs. dioxane was stirred with 142 mg. SeO2 24 hrs. at 80°,
filtered, and evapd. and the residue taken up in 30 ml. Me2CO and stirred with 0.50 ml. CrO3 5 min. at 20° to give mono-
O-mesyltrichothecolon (XVI). To the mother liquor was added 2 ml. 10N HCl and the mixt. kept 20 min. at 20° to give a
fraction contg. 8 mg. chlorohydrin of XVI. Trichocothelon (500 mg.) in 20 ml. pyridine treated with 8 ml. MeSO2Cl at 0° 3
hrs. gave XVI, m. 173-5°, [α]21 D 19° (c 0.88, CHCl3). Treatment of 100 mg. XVI with 1 ml. 10N HCl 15 min. at 20° gave
54 mg. chlorohydrin of XVI, m. 172-3°. Treatment of 261 mg. I in 11 ml. MeOH with 1.1 ml. concd. HCl 16 hrs. at 20°
gave 180 mg. XVII, m. 151-3°, [α]24 D 35 ± 2° (c 1.135, CHCl3). Treatment of 200 mg. I with 40 ml. 0.5N H2SO4 in 3:1
H2O-dioxane 16 hrs. at 20° gave 93 mg. XVIII, m. 155-7° (Me2CO-Et2O), [α]23 D 20 ± 1° (c 0.798, MeOH); tetra-O-Ac
deriv. [α]23 D 36 ± 2° (c 0.876, CHCl3). Treatment of 209 mg. IV in 40 ml. 0.5N H2SO4 in 3:1 H2O-dioxane 2.5 hrs. at 55°
gave 35 mg. XIX, m. 147-8° (Et2O-Petr. ether), [α]23 D 36 ± 2° (c 0.955, CHCl3). Similarly, 165 mg. IX gave 88 mg. XX,
[α]22 D 38 ± 2° (c 1.15, Me2CO). Refluxing 110 mg. IX in 25 ml. MeOH with 3 ml. HCl 3 hrs. gave 54 mg. XXI, m. 220°
(Me2CO-petr. ether), [α]23 D 56 ± 2° (c 1.055, MeOH). Treatment of 360 mg. di-O-Ac deriv. of IX in 6 ml. AcOH with 4 ml.
33% HBr in AcOH 4 hrs. at 55° gave 350 mg. XXII, [α]24 D 7 ± 1° (c 0.82, CHCl3). Reaction of 85 mg. I in 1.5 ml. pyridine
with 4 drops SOCl2 3 hrs. at 5° gave a dimeric cyclic sulfite, C30H40O10S2, m. 273-5° (Et2O), [α]24 D -60 ± 5° (c 0.318,
CHCl3). Treatment of 550 mg. XVII in 50 ml. Me2CO with 3.5 ml. CrO3 reagent followed by esterification with CH2N2
gave 55 mg. XXIII, [α]23 D -59 ± 2° (c 0.96, CHCl3). Treatment of 100 mg. VII in 4 ml. MeOH with 100 mg. Na2CO3 in 4
ml. H2O 10 min. gave 62 mg. XXIV, m. 132-3° (Et2O-pentene); O-Ac deriv. (XXV) prepd. Treatment of 60 mg. XXIV in 6
ml. pyridine with 128 mg. p-O2NC6H4COCl 23 hrs. at 20° gave 36 mg. XXVI, m. 180-2° (Et2O). Treatment of 2.75 g. VI in
50 ml. pyridine at -10° with 0.75 ml. SOCl2 30 min. gave 2.1 g. XXVII, m. 95-7° (C6H6-petr. ether), [α]24 D 35 ± 2° (c
0.943, CHCl3). To 2.1 g. XXVII in 150 ml. Et2O was added 1 g. LiAlH4 in portions at 0° and the mixt. refluxed 2.5 hrs.
with stirring to obtain 1.34 g. XXVIII, m. 160-1° (Et2O), [α]24 D 57 ± 2° (c 1.05, CHCl3). Oxidn. of 1.22 g. XXVIII with the
CrO3 reagent gave 620 mg. XXIX, m. 227-9° (Me2CO-Et2O-petr. ether), [α]24 D -59 ± 2° (c 0.977, CHCl3). Esterification
of 770 mg. XXIX with CH2N2 in Et2O gave 800 mg. XXX, m. 89-91° (Et2O-petr. ether), [α]24 D -34 ± 2° (c 0.92, CHCl3).
Hydrogenation of 150 mg. XXX in 20 ml. AcOEt in the presence of 100 mg. Pd-C at 22° until 2 equivs. H were consumed
gave 150 mg. XXXI, [α]29 D -94 ± 2° (c 0.99, CHCl3). Treatment of 100 mg. XXVIII in 1.5 ml. pyridine with 8 drops SOCl2
80 min. at 20° gave 40 mg. XXXII, m. 130-4° (petr. ether), [α]25 D 44 ± 2° (c 1.055, CHCl3). XXXII kept 4 hrs. with 10%
K2CO3 in 90% MeOH gave XXVIII. VI (250 mg.) and 30 ml. CF3CO2H kept 6 hrs. at 20° gave 112 mg. XXXIII, m. 110-
11° (pentane-heptane), [α]25 D -3 ± 2° (c 0.718, CHCl3), and 61 mg. XXXIV, m. 130-2° (Et2O-petr. ether), [α]25 D 44 ± 2°
(c 1.051, CHCl3). To 70 mg. XXXIII in 50 ml. Et2O was added LiAlH4 in excess at 0°, the mixt. refluxed 16 hrs., and the
isolated reaction product treated with CrO3 reagent to obtain 37 mg. XXXV, m. 114-16° (Et2O-petr. ether), [α]26 D -7 ± 2°
(c 1.125, CHCl3). Treatment of 72 mg. XXXIV in 25 ml. Me2CO with 0.1 ml. CrO3 reagent gave 31 mg. ketone (XXXVI),
m. 102-4° (Et2O), [α]22 D -3 ± 2° (c 0.98, CHCl3). To 345 mg. IV in 100 ml. CHCl3 was added 100 ml. H2O, the CHCl3
distd. within 30 min at 80° and the residue refluxed 6 hrs. to obtain 167 mg. XXXVII, m. 247-9° (Et2O). To 120 mg.
XXXVII in 1.8 ml. pyridine was added 0.45 ml. POCl3 at 0° and the mixt. kept 22 hrs. at 20° to obtain 85 mg. XXXVIII, m.
166-8° (Et2O). Hydrogenation of which (93 mg.) in 25 ml. AcOEt in the presence of 100 mg. 10% Pd-C gave 58 mg.
XXXIX, m. 180-2° (Et2O). Oxidn. of 204 mg. VI in AcOH with 100 mg. SeO2 in 90% AcOH (6 hrs., 80°) gave 130 mg. XL,
[α]22 D 51 ± 2° (c 1.194, CHCl3). Similarly, 500 mg. XXIII gave 290 mg. XLI (contg. 15% XXIII), [α]25 D 0.5 ± 2° (c 0.6,
CHCl3). XLI (250 mg.) in 40 ml. AcOEt was hydrogenated on 42 mg. Pd-C (normal conditions) 1 hr. (1.1 equivs. H was
consumed) to give 245 mg. dihydro deriv. (XLII) (contg. traces of XXIII), [α]27 D -7 ± 2° (c 1.2, CHCl3). To 206 mg. XLII in
3 ml. MeOH was added 7 ml. 10% NaOH (boiled 20 min. under N). The mixt. was warmed 4 min. at 90°, cooled to 0°,
adjusted to pH 1 with 2N H2SO4, extd. with Et2O, and washed with 2N NaHCO3 to give 3 mg. 2-methylcyclohexane-1,4-
dione, m. 45-6°. The NaHCO3 washing, acidified to pH 1 with H2SO4 and extd. with Et2O, gave 170 mg. acidic material,
which gave, (after esterification with CH2N2 in Et2O at 0°, 80 mg. crude Me 2-methyl-3-oxocyclopent-1-enecarboxylate
(XLIII) and 80 mg. amorphous material XLIII (80 mg.) in 3.5 ml. MeOH was kept with 2 ml. 2N K2CO3 15 hrs. at 22° to
give 70 mg. free acid of XXXXIII, m. 176-7° (Et2O). The amorphous material (80 mg.) gave, after repeated
chromatography on Al2O3, 15 mg. Me 2,5-dihydroxy-4-methylbenzoate (XLIV), m. 122-3° (C6H6-petr. ether. XLIV was
identical with a synthetic prepn. made by heating 16 g. toluhydroquinol and 25 g. KHCO3 in 40 g. glycerol 15 hrs. at 170°
under CO2 and esterifying the crude acid. Ir, uv, and N.M.R. spectra of most of the compds. are given.
~9 Citings
277. The incorporation of various substrates into acetylsulfanilamide and CO2 by pigeon liver slices
By Snyder, Robert; Schulman, Martin P.; Westerfeld, W. W.
From Archives of Biochemistry and Biophysics (1964), 108(2), 215-20. Language: English, Database: CAPLUS,
DOI:10.1016/0003-9861(64)90378-9
14C-labeled EtOH, acetate, pyruvate, or butyrate added to pigeon liver slices in the presence of sulfanilamide contributed
about 70, 50, 45, and 20%, resp., of the acetyl groups found in the acetylsulfanilamide. The simultaneous addn. of
unlabeled alc. or acetate reduced the incorporation of 14C from pyruvate or butyrate, while the simultaneous addn. of
unlabeled pyruvate, glycerol, or butyrate did not seriously reduce the incorporation of 14C from EtOH or acetate. Some
15 times as much 14C from butyrate was found in the CO2 as in the acetylsulfanilamide; the corresponding ratios for
pyruvate, acetate, and alc. were 3, 1/2, and 1/3, resp. The oxidn. of labeled butyrate and pyruvate was not seriously
decreased by the simultaneous presence of unlabeled EtOH or acetate, but the oxidn. of acetate and EtOH was inhibited
by pyruvate and esp. butyrate. The results are interpreted to show a compartmentation of the acetyl CoA formed from
the different substrates with a preferential utilization of alc. and acetate for the acetylation reaction, and a preferential
oxidn. of butyrate and pyruvate.
~0 Citings
278. The binding of ions and the shortening of glycerol-treated muscle fibers
By Bowen, William J.; Martin, Harold L.
From Biochemical and Biophysical Research Communications (1964), 16(2), 129-34. Language: Unavailable,
Database: CAPLUS, DOI:10.1016/0006-291X(64)90349-3
Expts. were performed in which the models of contraction (glycerol-treated rabbit psoas muscle fibers) were methylated
and acetylated before use as an enzyme or as a model of contraction. Muscle fibers were either acetylated by repetitive
addns. to the 10 ml. incubation medium of 5 µl. of Ac2O at intervals of approx. 5 min. for 1 hr. while the pH was
maintained at 8 by addns. of NaOH, or were methylated by the addn. of Me2SO4 at pH 4.2, maintained by 0.1M Na
acetate. Methylations were carried out overnight. The isotonic contractions produced by addns. of adenosine
triphosphate (ATP) and other compds. in these fibers and in untreated normal fibers were studied while they were
stretched out on glass microscope slides resting on a millimeter scale. Acetylation, which covers the amino groups of the
actomyosin and makes the protein anionic, inhibited ATP-induced shortening 80% compared with controls. Methylation,
which covers the carboxyl groups and makes the protein cationic, inhibited ATP-induced shortening to only 40% of the
controls. The extent of coupling of the splitting of ATP by acetylated and methylated fibers to the ATP-induced
shortening of similarly treated fibers is not direct because acetylation barely affected splitting by fibers, while methylation
inhibited it ≥99%. Substances such as Na pyrophosphate which caused no contraction of normal fibers and which ionize
to form polarized ions caused shortening of methylated fibers. Substances like CaCl2 which caused shortening of normal
fibers did so much more effectively with acetylated fibers. ATP caused shortening of methylated fibers although the
evidence for splitting of ATP by the same fibers is almost nil.
~0 Citings
279. Steroids. XXXI. Aldol condensation of corticoids with formaldehyde. 2. 21-Hydroxymethylation of

Reichstein's substance S, dexamethasone, and deoxycorticosterone
By Noguchi, Shunsaku; Nakayama, Fujiko; Morita, Katsura
From Chemical & Pharmaceutical Bulletin (1964), 12(10), 1180-3. Language: English, Database: CAPLUS,
DOI:10.1248/cpb.12.1180
cf. CA 60, 4207c. Reichstein's substance S (10 g.) in 100 ml. MeOH, 300 ml. 37% HCHO, and 30 g. NaOAc was
refluxed 1.5 hrs. to give 3.6 g. 21-hydroxymethyl-17α,21-dihydroxypregn-4-ene-3,20-dione (I), m. 160°, [α]20 D 102° (c
1.1, EtOH). On acetylation, 1 g. I gave 0.8 g. 21-acetoxymethyl-17α-hydroxy-21-acetoxypregn-4-ene-3,20-dione (II), m.
170-200°. Similarly, 1.5 g. dexamethasone gave 1 g. 21-hydroxymethyldexamethasone, m. 220-5°, [α]23 D 87° (c 1,
pyridine). The results were slightly different when the 17α-OH group was absent. Thus, 10 g. deoxycorticosterone gave
2.8 g. 21-hydroxymethyldeoxycorticosterone (III), m. 132-4°, [α]22 D 196° (c 0.53, EtOH), and 2.2 g. 21,21-
bis(hydroxymethyl)deoxycorticosterone, m. 185-90°, [α]22 D 133° (c 0.35, EtOH). Acetylation of 200 mg. III gave 240 mg.
the 21,22-diacetate (IV), m. 100-200°. A soln. of 500 mg. II in benzene was passed through a column of 25 g. Al2O3 and
the column eluted with benzene and 4:1 benzene-ether to give 200 mg. 21-methyl-17-hydroxypregn-4-ene-3,20,21-trione
acetate, m. 149-55°, [α]20 D 34° (c 1.3, CHCl3); N.M.R. spectrum was described. Similarly, a soln. of 200 mg. IV in
benzene was passed over 20 g. Al2O3 to give 100 mg. amorphous product which failed to crystallize. Its structure as 21-
methylpregn-4-ene-3,20,21-trione (V) was based on its N.M.R. spectrum. When V was allowed to stand at room temp. in
air for several days most of it decompd. to give androst-4-ene-3,17-dione. The uv and ir spectra of all the compds. were
described.
~0 Citings
280. Quantitative gas-liquid-chromatographic determination of free glycerol in blood serum

By Jellum, E.; Bjornstad, P.
From Journal of Lipid Research (1964), 5(3), 314-17. Language: Unavailable, Database: CAPLUS
Levels of free glycerol (I) in serum were detd. by gas-liquid chromatography using butane-1,4-diol (II) as internal
standard. After addn. of II, the serum was treated with phosphotungstic acid, and I and II in the ext. were acetylated with
Ac2O. The acetates were extd. with Et2O, and finally chromatographed at 150-190° using butanediol succinate as
stationary phase. Levels of I in normal serum were 0.4-1.2 mg./100 ml. The method with a range of ±5-10% could be
used for as little as 0.1 mg./100 ml.
~4 Citings
281. Properties of organic-water mixtures. I. Activity coefficients of sodium chloride, potassium chloride, and
barium nitrate in saturated water mixtures of glycol, glycerol, and their acetates. Model solutions for
hyperfiltration membranes
By Kraus, Kurt A.; Raridon, Richard J.; Baldwin, Willis H.
From Journal of the American Chemical Society (1964), 86(13), 2571-6. Language: Unavailable, Database: CAPLUS,
DOI:10.1021/ja01067a010
The soly. of NaCl in mixts. of H2O with ethylene glycol, its mono- and diacetates, glycerol, and its mono-, di-, and
triacetates was detd. at 25° by packed column techniques. The solubilities of KCl and Ba(NO3)2 were detd. for H2O
mixts. of glycol, glycerol, and the corresponding fully acetylated compds. Miscibility limits were established in the
presence and absence of salts. From the soly. data activity coefficients γ±(0) of the salts were computed using the same
reference states as for aq. solns. and expressing concns. in moles/kg. of H2O. While the values of γ±(0) in the glycol-
and glycerol-H2O mixts. were usually less than for the 2-component aq. solns., they increased with the fraction of OH
groups acetylated and were > 1000 times larger for the fully acetylated compds. at low H2O content.
~14 Citings
282. New types of neutral lipids

By Bergel'son, L. D.; Vaver, V. A.; Prokazova, N. V.
From Doklady Akademii Nauk SSSR (1964), 157(1), 122-4. Language: Unavailable, Database: CAPLUS
The triglyceride fractions isolated from corn and sunflower oils, sheep fat, codliver oil, and yeast were subjected to gas-
chromatographic examn. and were found to contain, besides the expected esters of glycerol, esters of 1,3-butanediol,
1,4-butanediol, 2,3-butanediol, 1,2-propanediol, (CH2OH)2, 1,3-propanediol. The amts. of these varied from specimen to
specimen (results tabulated for diacetates formed by redn. with LiAlH4 and acetylation with Ac2O). The normal acid
components of these esters were found to be palmitic, oleic, and linoleic acids, as well as stearic acid.
~0 Citings

283. Improved determination of glycerol and fatty acids in glycerides and ethanolamine phosphatides by gas-
liquid chromatography
By Holla, K. S.; Horrocks, Lloyd A.; Cornwell, David G.
Fatty acid and glycerol contents of glycerides were estd. by hydrogenolysis-acetylation procedures and gas-liquid
chromatography. Preliminary acetolysis was necessary for the estn. of glycerol in ethanolamine phosphatides.
~0 Citings
284. Improved determination of cholesterol and fatty acids in glycerides and ethanolamine phosphatides by gas-
liquid chromatography
By Holla, K. S.; Horrocks, Lloyd A.; Cornwell, David G.
Fatty acid and glycerol contents of glycerides were estd. by hydrogenolysis-acetylation procedures and gas-liquid
chromatography. Preliminary acetolysis was necessary for the estn. of glycerol in ethanolamine phosphatides.
~0 Citings
285. Gas chromatographic analysis of a mixture of polyols

By Anzhele, P. G.; Vasyunina, N. A.; Balandin, A. A.; Leibnits, E.
From Molekulyarnaya Khromatografiya (1964), 61-5. Language: Russian, Database: CAPLUS
Mixts. of HOCH2CH2OH, HOCH2CH2OMe, glycerol, ethyritol, xylitol, and sorbitol, resulting as hydrogenolysis products of
monoses were analyzed after acetylation by gas chromatography. Reflux 3 g. of the sample for 25 min. with 24 ml. of
freshly distd. Ac2O then add 5 ml. boiling H2O and refluxing an addnl. 3-5 min., and finally add 50 ml. boiling H2O. Ext.
the acetyl derivs. with C2H4Cl2 and evap. the solvent. The efficiency of the acetylation was proved by ir spectral detn. of
the OH group. The samples were analyzed on columns, 2 m. × 0.6 cm., packed with an inert material (Sterchamol 0.25-
0.4 mm.) impregnated with the polyester of succinic acid and diethylene glycol (15% by wt.) operated at 200° and flow
rate of 33 ml. H/min. The temp. of the sample evaporator was 350-400°. Prior to the detn., the column was rinsed with H
at 50 ml./min. at 220° for 10 hrs. after removing the catharometer. The retention time of analyzed compds. are given.
The relative error was 0.1-0.9%.
~0 Citings
286. Film of plasticized amylose

From No Corporate Source data available (1964), NL 6406933 19641221, Language: Unavailable, Database: CAPLUS
The replacement of glycerol (I) by 10-30% poly(vinyl alc.) (II) contg. <20% acetylated groups as plasticizer gives amylose
(III) films having improved mech. characteristics; III contains preferably <20% amylopectin. Thus, 8 g. fat-free maize III
was dissolved in 72 g. hot H2O and the soln. cooled to 95°, was introduced into a soln. of 2 g. II (<2% acetate groups) in
48 g. H2O at 95°. After 60 sec. mixing, the compn. was applied on a glass plate coated with lecithin and preheated at
95°. After drying and hardening, the film was removed and aged at 23° and 23 and 50% relative humidity for 1 week.
Films were also prepd. from III alone and from a mixt. contg. 8 g. III and 2 g. I. After aging, the following characteristics
were obtained for 20-5 µ films: tensile strength 0.631, 0.227, 0.595 kg./cm.2 (films aged at 50% rel. humidity) and 0.924,
0.629, 1.033 kg./cm.2 (films aged at 23% rel. humidity); elongation at break 5,12,13% (50% rel. humidity) and 8,6,12%
(23% rel. humidity); tearing strength 171, 134,312 g./0.01 mm. (50% rel. humidity) and 169, 176, 379 g./0.01 mm. (23%
relative humidity) for the film without plasticizer, the film with I, and the film contg. II, resp.
~0 Citings
287. Estimation of glycerol and diglycerol in the presence of each other

By Hartman, L.
From Journal of Chromatography (1964), 16(1), 223-5. Language: English, Database: CAPLUS, DOI:10.1016/S0021-
9673(01)82463-8
Glycerol and diglycerol are detd. in the presence of each other by gas chromatography of their acetates. Weigh 0.1-0.5
g. of com. monoglyceride or other glyceride mixt. and saponify with KOH-EtOH or MeOH soln. in the usual way. After
removing most of the alc. in vacuo acidify the mixt. with HOAc. Ext. the liberated fatty acid with CHCl3. Heat the aq.
layer in vacuo below 100° to evap. most of the H2O. Add 25 g. of Ac2O to the residue (or to 1 g. of known glycerol and
(or) diglycerol mixt.) and reflux for 2 hrs. Remove the excess acetylating agent in vacuo at 100°. Dissolve the product in
a little Et2O and wash with H2O. Dry the Et2O soln. with anhyd. Na2SO4 and evap. the Et2O in vacuo. Analyze the mixt.
on a 6.5 mm. diam. X 240-cm. long column of 0.25% silicone high vacuum grease or 0.5% silicone rubber gum SE-30 on
0.177-mm. diam. (ASTM 80) glass beads, in a gas chromatograph fitted with an Ar ionization detector operating at 207°.
Me stearate served as reference compd. to det. relative retention times. The relative retention times of the esters on
silicone grease and on the SE-30 columns were: glycerol triacetate, 0.081 and 0.067, diglycerol tetraacetate, 0.516 and
0.486, resp.
~0 Citings
288. Cholinesterase of Pseudomonas fluorescens. III. Acetyltransferase activity

By Fitch, Walter M.
From Journal of Biological Chemistry (1964), 239(5), 1328-34. Language: Unavailable, Database: CAPLUS
cf. CA 59, 14236e. The inducible cholinesterase of P. fluorescens was found to catalyze the transfer of the acetyl group
of the substrate to suitable alc. acceptors. Such transferase activity was as much as 12 times more rapid than the
esterase activity when AmOH was the acceptor. Acceptors were more suitable as they became longer and less
branched. Primary alcs. were better acceptors than secondary or tertiary alcs. The presence or absence of a pos.
charge did not affect acceptor activity. The kinetics were studied and found to be consistent with the acceptor alc. adding
onto the acyl-enzyme complex. The alc. may also bind with the free enzyme and produce a competitive inhibition.
Evidence is presented which indicates that the acceptor- and ester-binding sites may not be the same.
~0 Citings
289. Structure of betanin. VII. Structure of the bark pigment betanin

By Wilcox, M. E.; Wyler, H.; Mabry, T. J.; Dreiding, Andre S.
From Helvetica Chimica Acta (1965), 48(1), 252-8. Language: German, Database: CAPLUS
cf. CA 59, 11418b. Treatment of I (R = glucosyl, R' = H) (II) with CH2N2 and subsequent acidic hydrolysis and
acetylation yielded III (R = Ac, R' = Me) (IV), which cleaved by alkali, esterified with MeOH, and oxidized with K
isonitrosodisulfonate (V) gave 5-hydroxy-6-methoxy-2-carbomethoxyindole (VI), demonstrating the attachment of the
glucosyl group in II (betanin) to the 5-OH group. The 5-position of the free OH group in VI was proved by an unequivocal
synthesis. Electrophoretically pure K salt (120 mg.) of II, 5 cc. CF3CO2H, and 0.5 cc. AcCl evapd., the residue
resuspended in 20 cc. AcOK-AcOH buffer (pH 4.5) contg. 5 g. AcOK and 3.5 cc. AcOH/l., filtered off, dissolved in 10 cc.
buffer and 0.5 cc. 0.5N KOH, and subjected 26 hrs. to electrophoresis on a paper column at 100 v./55 mamp., and the
eluate of the zone which had migrated 60 cm. concd. to 5 cc., acidified with 1.3 cc. 6N HCl, and filtered yielded 35 mg.
acetylated II, Rf 1.08 (0.05M C5H5N.HCO2H on paper), 0.9g (0.1M HCO2H on paper). II (670 mg.) in 100 cc. abs. MeOH
treated with CH2N2 under N from 12 g. p-MeC6H4-SO2NMeNO, the soln. cooled with liquid air, evacuated to 0.005 mm.,
and heated 3 hrs. at 50° yielded 65 mg. III (R = H, R' = Me), m. 165-8° (CH2Cl2-MeOH). The crude hydrolyzate from a
similar run with 1 g. II, 150 cc. MeOH, and CH2N2 from 18 g. p-MeC6H4SO2NMeNO yielded with Ac2O-C5H5N 65 mg. IV,
m. 239-40° (CH2Cl2-MeOH). IV (0.095 g.), 7 cc. H2O, and 0.64 g. KOH degassed, heated 8 hrs. at 70-80°, treated with 4
cc. 2.66N H2SO4, and evapd., the residue heated 4 hrs. at 60-70° with 12 cc. N HCl, treated with 0.2 g. V in 5 cc.
Soerensen buffer (pH 8), dild. after 2 min. with AcOEt, and treated after an addnl. 5 min. with 0.5 g. Na2S2O4, and the
crude product sublimed at 90-105°/0.005 mm. gave 6 mg. 4-methyl-2,6-dicarbomethoxypyridine, m. 122-4°, and 2 mg.
VI, m. 178-80°, Rf0.85 (4:1:5 BuOH-AcOH-H2O). II (1 mg.) in 1 cc. buffer contg. 3.95 g. AcONa, 3 g. AcOH, and 20 cc. N
NaOH/l. incubated at 38° with emulsin showed after 10, 20, 30, and 60 min. about 30, 50, 70, and 95% hydrolysis, resp.
In a similar run with cellulase only about 30% of the II was hydrolyzed after 1 hr. Hydantoin (8 g.), 15 g. isovanillin, 16 cc.
glycerol, and 4 cc. morpholine heated 4 hrs. at 160° yielded 16.7 g. 3-hydroxy-4-methoxybenzalhydantoin (VII), m. 277-
80° (AcOH). VII (16 g.) in 50 cc. 4N NaOH shaken with 450 g. 2% Na-Hg gave 11.5 g. 3-hydroxy-4-
methoxybenzylhydantoin (VIII), m. 194°(H2O). VIII (10 g.) and 90 g. Ba(OH)2 in 40 cc. H2O refluxed 24 hrs. and
neutralized gave 6.7 g. 3-hydroxy-4-methoxyphenylalanine (IX), m. 271-2°. IX treated with SOCl2 and MeOH gave the
oily Me ester (X) of IX. X (0.75 g.) in 80 cc. H2O treated with stirring at room temp. with 60 cc. AcOEt, 1.54 g. v, and 0.56
g. NaHCO3 in H2O and satd. after 0.5 hr. with NaCl gave 0.43 g. VI, m. 181-2°; acetate m. 225-6° (EtOH).
~7 Citings
290. Quantitative determination of monosaccharides and their acetates by gas liquid chromatography
By Sawardeker, Jawahar S.; Sloneker, James H.; Jeanes, Allene
From Anal. Chem. (1965), 37(12), 1602-4. Language: English, Database: CAPLUS, DOI:10.1021/ac60231a048
Mixts. contg. up to 10 monosaccharides were analyzed by gas chromatography of the derived alditol acetates. Sugar
mixts. were treated 3 hrs. with aq. NaBH4, HOAc was added, the soln. was evapd., the residue was refluxed 4 hrs. with
Ac2OC5H5N, and the soln. injected directly into a gas chromatograph having a flame ionization detector, disk integrator,
and modified injection port. Completely acetylated glycerol, erythritol, rhamnitol, fucitol, ribitol, arabinitol, xylitol, mannitol,
galactitol, and glucitol were completely sepd. on a 10-ft. column contg. 3% ECNSS-M stationary phase at 190°; a 4-ft.
column of 10% Carbowax 20M terminated with terephthalic acid, at 190°, sepd. all but the last 2 derivs. The redn. and
acetylation are quant., and no decompn. occurred on the column.
~371 Citings
291. Paper electrophoresis of steroids in borate buffers

By Blank, R. H.; Hausmann, W. K.; Holmlund, C. E.; Bohonos, N.
9673(00)99905-9
The rate of anodic migration of steroids contg. hydroxyl groups of C-20 and C-21 was dependent upon pH with migration
increasing with alky.; all complexing steroids streaked below pH 7.0. Anodic migration of 16α,17αdihydroxy steroids was
prevented by acetylation of 1 of the cis hydroxyl groups. 16α-Hydroxylated steroids contg. a 17βhydroxy group or that
did not have an O group at C-17 showed slight cathodic migration. The presence of a C-20 ketone enhanced anodic
migration of 16α,17α-hydroxy steroids. Steroids contg. a glycol or glycerol side chain migrated toward the anode more
slowly than 16α,17α-hydroxy steroids. 1,3-Cis-oriented hydroxy groups caused steroids to remain stationary; 1,3,5-cis
groups migrated at pH 9.3.
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292. Organic derivatives of phosphorus isocyanates

By Fielding, Harold C.
The title compds. are used to coat surfaces such as glass-reinforced plastics and as additives to synthetic fibers to
increase fire resistance as well as the ease of dyeing and to add antistatic properties. Phosphoryl triisocyanate (I) 5 was
added with stirring to dry BuOH 20 parts and cooled in a water bath. After 0.5 hr., excess BuOH was removed in vacuo
and the residue recrystd. (hot H2O) to yield 5 parts of tributylphosphorylurethan, P(NHCO2Bu)3, m. 149°. Similarly prepd.
was triallylphosphorylurea, m. 190°. This polymerizes with Bu perbenzoate in HCONMe2 to a hygroscopic polymer. I
polymerizes with dimethylglyoxime to form a white solid and forms a polymer with hexamethylene glycol. I also
polymerizes with hexamethylaminediamine and forms a white rubbery polymer with diethylene glycol pentaerythritol
adipate. I with a glycerol-propylene oxide condensate forms a hard white polymer and a semi-rigid polyurethan foam
with a branched poly(diethylene adipate). I gives a polymer with castor oil. When 1 group of I is blocked by BuOH, the
diisocyanate gives a polymer with a glycerol/propylene oxide condensate. With PhOH I forms
triphenylphosphorylurethan(II), m. 153°. II with diethylene glycol pentaerythritol adipate forms a rubbery polymer and
with paraformaldehyde, a hard brittle polymer. P(NCO)3 homopolymer with a branched poly(ethylene adipate) forms a
hard crosslinked polymer. I with partially acetylated cellulose forms a polymer insol. in org. solvents; this can be pressed
into flame-retardant films. I with collodion forms films that are not as inflammable as cellulose.
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293. Normal and abnormal orientations in the substitution reactions of 1,2,3-trisubstituted benzenes. I.
Acetylation of hemimellitene
By Buu-Hoi, N. P.; Jacquignon, Pierre; Roussel, Odette
From Bulletin de la Societe Chimique de France (1965), (2), 322-6. Language: French, Database: CAPLUS
1,2,3-C6H3Me3 (I) with AcCl and AlCl3 yielded a mixt. of 3,4,5- (II) and 2,3,4-Me3C6H2Ac (III). I (30 g.) and 22 g. AcCl in
500 cc. petr. ether refluxed 3 hrs. with 40 g. powd. AlCl3 yielded 85% mixt., b20 145-50°, which by vapor phase
chromatography gave a trace unidentified trimethyl-acetophenone, III, b. 258-60° [oxime m. 111-12° (cyclohexane)], and
II, b. 260-4°, n21.8 D 1.5451 [oximc m. 152° (cyclohexane)]. The ketone mixt. refluxed 3 hrs. with excess NH2OH in EtOH
gave a mixt. of the oximes of II and III, which was fractionated from EtOH and cyclohexane. The oxime of II refluxed 3
hrs. with HCl gave quant. II. The oxime of III yielded similarly 2,3,4-Me3C6H2NH2.HCl (IV.HCl) which basified with aq.
NaOH gave the pale yellow, oily IV, b20 136-40° [N-Ac deriv. (V) m. 140° (aq. EtOH)]. IV (1 g.) in dil. H2SO4 treated below
20° with 1 g. NaNO2 and then heated with dil. H2SO4 on a steam bath gave 2,3,4-Me3C6H2OH, m. 69° (petr. ether). The
oxime of II in Et2O treated at 0° during 0.5 hr. with PCl5 yielded 80% 3,4,5-Me3C6H2NHAc (VI), m. 165-6°, which
hydrolyzed with concd. HCl gave 3,4,5-Me3C6H2NH2 (VII), b16 133-5°, m. 79-80°. VII diazotized and heated with dil.
H2SO4 gave 3,4,5-Me3C6H2OH, m. 107°. The oxime of III treated with PCl5 gave a mixt. of VI, m. 165-6°, and V, m. 139-
40°. VII and 2,3-dichloro-1,4-naphthoquinone (equimolar amts.) in EtOH refluxed 0.5 hr. with 1.5 mole equivs. AcONa
yielded 2-(3,4,5-trimethylanilino)-3-chloro-1,4-naphthoquinone (VIII), bordeaux-red, m. 207° (EtOH). IV gave similarly the
2-(2,3,4-Me3C6H2-NH) analog (IX) of VIII, dark red, m. 182° (EtOH). VIII and IX gave a violet soln. in concd. H2SO4. VIII
(4 g.), 9 g. glycerol, 5 cc. concd. H2SO4, and 4 g. As2O3 gave by the general Skraup procedure 2 g. 5,6,7-
trimethylquinoline, m. 83° (hexane), b24 174-7°; picrate m. 216° with decompn. above 190° (EtOH). IV (0.5 g.), 0.4 g.
Ac2CH2, and 2 drops AcOH refluxed 1.5 hrs., and the resulting anil heated with H2SO4 on a water bath yielded 0.5 g.
2,4,5,6,7-pentamethylquinoline, m. 94-5° (aq. MeOH); picrate m. 204-5° with decompn. above 180° (C6H6). IV (6 g.), 4.5
g. 2-C10H7OH, and 0.1 g. iodine heated 12 hrs. at 200-30° yielded 75% N-(3,4,5-trimethylphenyl)-2-naphthylamine, m.
116° after previous melting at 95° and subsequent resolidification, b13 255-8°; it gave a violet picrate which decompd.
upon recrystn. A similar run with 1-C10H7OH at 250° yielded 45% N-(3,4,5-trimethylphenyl)-l-naphthylamine (X), yellow-
amber oil, b17 255-6°. X in Ac2O heated with ZnCl2 gave an unidentified material, m. 172° (MeOH), which contained an
Ac group. II-III mixt. (5 g.) treated with stirring with aq. NaOBr from 5 cc. Br and 10 g. NaOH in 20 cc. iced H2O and then
with aq. NaHSO3, and the mixt. acidified with dil. H2SO4 yielded about 70% 3,4,5-Me3C6H2CO2H, m. 215°, and 2,3,4-
Me3C6H2CO2H, m. 167°, which were sepd. by fractional crystn. from H2O. II (16.2 g.), 17 g. KOH, and 14.7 g. isatin in
about 100 cc. EtOH refluxed 24 hrs. gave more than 90% 4-CO2H deriv. of 2-(3,4,5-trimethylphenyl)quinoline (XI), very
pale yellow, m. 254° with decompn. above 235° (EtOH), which heated above its m.p. gave X, m. 106° (EtOH); picrate m.
237° (sublimed above 170°, decompn. above 215°) (PHCl). 4,5,1,2,3-(O2N)2C6HMe3, m. 96°, condensed with
chrysenequinone in refluxing AcOH yielded 5,6,7(or 6,7,8)-trimethylchryseno[5',6':2,3]quinoxaline, pale yellow, m. 273°
(PhNO2); indigo-blue in concd. H2SO4. 4,5,-1,2,3-(H2N)2C6HMe3 (XII) and Bz2 refluxed 1 day in EtOH gave an
unidentified compd., yellowish needles, m. 252° (EtOH). XII with Bz2 in Me2NPh gave yellow prisms, m. 191° (EtOH):
red-orange in concd. H2SO4. XII treated with Ac2O in the presence of a few cc. EtOH gave a compd. C13H18N2O2,
needles,m. 316° with sublimation above 260°.
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294. New synthesis of 1-1-(O-benzyl)glycerol

By Lands, William E. M.; Zschocke, Albrecht
From Journal of Lipid Research (1965), 6(2), 324-5. Language: English, Database: CAPLUS
Pure l-1-O-benzylglycerol, D(-)-α-benzylglycerol (I), was prepd. in 3 steps from d-3-O-benzylglycerol, L(+)-α-
benzylglycerol) (II). The good agreement between the optical activities of the isomers I and II and between their isomeric
diacetates indicates that this method can be useful for prepg. pure glycerolipids. Removal of the "blocking group" can
give 2,3-disubstituted derivs. contg. free hydroxyl groups at the C-1 position. A cooled soln. of 22.5 g. II ([α]D 5.85°) in
20 ml. dry C5H5N was treated with a soln. of 47.5 g. p-MeC6H4SO2Cl in 80 ml. dry C5H5N for 1 hr. After 36 hrs. at
room temp., Et2O was added, the C5H5N was washed out, and the Et2O soln. was dried and concd. to an oil which gave
46 g. 1,2-di-p-toluenesulfonyl-3-O-benzylglycerol (III), m. 54-6° (Et2O at -20°). A soln. of 20.15 g. III in 250 ml. anhyd.
EtOH and 16.1 g. KOAc were refluxed for 30 hrs. The cooled mixt. was filtered. Work up of the filtrate gave 6.75 g. 2,3-
diacetyl-1-O-benzylglycerol (IV) (contg. some partially solvolyzed IV). Hydrolysis of 6.75 g. crude IV in 50 ml. 95% EtOH
contg. 2.03 g. NaOH for 30 min. at 50° gave an oil. Distn. yielded 3.1 g. I, b0.15 140-2°, [α]D -5.85°. II (9.1 g.) and 12.2
g. Ac2O were dissolved in 50 ml. C6H6 and 0.09 ml. 70% HClO4 was added with cooling. After 3 hrs. at room temp., the
soln. was dild. with Et2O and treated with H2O. Distn. of the residue from the H2O-washed, dried, and concd. Et2O
layer gave 6.7 g. of a fraction with b1.75 135-9°. Redistn. gave 1,2-diacetyl-3-O-benzylglycerol, b0.6 143-5°, [α]D
17.25°. Similarly, acetylation of I gave 2,3-diacetyl-1-O-benzylglycerol, b0.15 140-3°, [α]D -17.25°.
~1 Citing
295. Modification of amino acid acceptance and transfer capacity of s-RNA in the presence of organic solvents
By Sarin, P. S.; Zamecnik, P. C.
From Biochemical and Biophysical Research Communications (1965), 19(2), 198-203. Language: English, Database:
CAPLUS, DOI:10.1016/0006-291X(65)90504-8
Aminoacetylation of Escherichia coli s-RNA in the presence of org. solvents was studied. The amino acid acceptance
capacity of aspartyl-s-RNA was increased in the presence of ethylene glycol monomethyl ether (I), 1 and 5% diethylene
glycol, propylene glycol, glycerol, benzene, toluene, and decalin. The lysine acceptor capacity was decreased by all
solvents except I, but particularly by benzene, toluene, and decalin. Valine acceptor capacity was only slightly affected
by org. solvents. Aminoacetylation of s-RNA with phenylalanine, leucine, and lysine was inhibited in the presence of
benzene, toluene, and decalin, but aminoacetylation with valine, tyrosine, and aspartic acid was only slightly affected.
The cell-free E. coli system was studied in the presence of 5 and 10% I. At 5%, I stimulated polyuridine-directed
polyphenylalanine synthesis by 150%, but at 10%, I, inhibited polyphenylalanine synthesis by 60%. The inhibition
caused by a high concn. of I was reversed by the addn. of more polyuridine. The influence of org. solvents on the
various components of the amino acid acceptor and transfer systems was measured by optical rotary dispersion.
Amplitude increases indicating an ordering of the structure were noted in ribosomes, valyl synthetase, and s-RNA in the
presence of I. An amplitude decrease implying an opening up of the secondary structure was noted with polyuridine.
The effect of org. solvents on amino acid acceptor and transfer systems consisted of modifications of the enzyme,
ribosomes, and s-RNA.
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296. Initiators for formaldehyde polymerization

By Sidi, Henri
CAPLUS
The initiators, used in amts. of 0.001-0.05 part/part HCHO, are esters of mono- or polyhydric aliphatic alcs. with
epoxidized drying oils, e.g. tall oil, soybean oil, or linseed oil. The process is best carried out in a hydrocarbon medium.
Thus, the HCHO from pyrolysis of 100 parts α-polyoxymethylene was swept with a slow N stream through a series of
traps, 1 at room temp., 1 at 0° and 2 at -15 to -25°, and then into a vessel at 25-30° contg. cyclohexane (I) 1500,
phenothiazine 0.1, and pentaerythritol tetraester of epoxidized tall oil fatty acids (oxirane O content 5.56%) 5 parts. The
mixt. was stirred during the reaction. After polymerization was complete, the product was filtered, washed with 300 parts
I, and dried at 65° to const. wt. The yield was 56.7 parts, inherent viscosity 2.06 at 150° (0.5% in HCONMe2 contg. 1%
Ph2NH). Such polymers are very tough and can be fabricated into useful articles by melt extrusion, injection, or
compression molding.
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297. Individual molecular species of different phospholipid classes. II. A method of analysis
By Renkonen, Ossi
From Journal of the American Oil Chemists' Society (1965), 42(4), 298-304. Language: Unavailable, Database:
CAPLUS, DOI:10.1007/BF02540133
The conversion to diglyceride acetates (I) provided a route to analysis of fatty acids in many phosphatidyl compds., which
had been obtained previously as mixts. with alkoxy analogs. The I are prepd. by acetolysis with (a) mixt. of acetic
anhydride and HOAc or (b) by treatment with phospholipase followed by acetylation. Acetolysis was used successfully
with phosphatidyl choline, phosphatidyl ethanolamine and corresponding alkoxy phosphatide (native cephalin B),
phosphatidyl serine, phosphatidyl inositol, phosphatidyl glycerol, phosphatidic acid, and cardiolipin. Phospholipase C
from Clostridium welchii was used for native choline and ethanolamine plasmalogens as well as for sphingomyelins. The
I obtained from lecithins of eggs, ox brain, and human serum were fractionated by thin-layer chromatography on
Kieselgel G-AgNO3 and the fractions characterized by gas-liquid chromatography. Data thus obtained in combination
with enzymic analyses of the acids at α- and β-positions of the mols. makes possible a detailed description of lecithins.
Cf. CA 60, 16189f. 27 references.
~8 Citings
298. Identification of components in the polyester urethans and in modified polyesters

By Li gotti, I.; Bonomi, G.; Piacentini, R.
From Rassegna Chimica (1965), 17(4), 137-43. Language: Italian, Database: CAPLUS
Shredded polyurethan and polyester samples (0.5-1.5 g.) were hydrolyzed by heating with concd. KOH (3 g. in 2 ml.
water) to 350° under a N blanket. Diamines and polyols were collected in a tube kept in an ice bath; dicarboxylic acids
remained in the flask and were esterified with MeOH in the presence of 4% H2SO4. Diamines and polyols were sepd. in
a separatory funnel by using ether as the solvent. Gas-chromatographic analysis of a sample by using Chromosorb W
impregnated with Apiezon L showed 2,4- and 2,6-toluenediamine, 1,5-naphthalenediamine, 4,4'-
diaminodiphenylmethane, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, and 3,3-dichloro-4,4-
diaminobiphenyl. Polyols were acetylated with Ac2O and then chromatographed through Chromosorb W60 impregnated
with Carbowax 20M. A typical sample contained 2,3-butanediol, 1,2-propanediol, ethylene glycol, 1,6-hexanediol, 1,3-
butanediol, diethylene glycol, glycerol, and trimethylpropanol. Esterified dicarboxylic acids were chromatographed as
polyols and also by using silicone rubber SE 30 as the impregnant. Tere-, iso-, and o-phthalic, sebacic, azelaic, and
adipic acid were identified in a sample. Phenolic compds. were acidified, dissolved in acetone, and sepd. on a thin-layer
chromatogram by using Woelm polyamide as a coating. The developer was 0.5N alc. KOH. The Rf values for
hydroquinone and naphthol were 0.75 and 0.55.
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299. Hydrolysis of 1,2-diglyceride acetates with pancreatic lipase

By Renkonen, Ossi
From Annales Medicinae Experimentalis et Biologiae Fenniae (1965), 43(3), 194-9. Language: English, Database:
CAPLUS
Diglyceride acetates were first prepared from the lecithins derived from hen eggs and ox brain by hydrolysis with
phospholipase C and subsequent acetylation. Partial hydrolysis of these prepns. with pancreatic lipase (I) revealed that
the long chain satd. fatty acids esterified on C-1 of glycerol were removed much faster than the unsatd. fatty acids on C-
2. Diglyceride acetates were then prepd. from phosphatidylinositol of ox heart by a similar procedure, and subsequent
hydrolysis with I showed that these compds. have mainly satd. fatty acids on the C-1 of the glycerol moiety, and unsatd.
fatty acids on C-2. On the other hand, hydrolysis of these diglyceride acetates with phospholipase A of Crotalus
adamanteus resulted in the unsatd. fatty acids being liberated, thus proving that this enzyme specifically hydrolyzes the
ester bond at C-2. The techniques developed provide a micromethod for the analysis of the positional distribution of fatty
acids in 1-2 dliglyceride acetates.
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300. Gas chromatographic determination of glycerol

By Balakhontseva, V. N.; Poltinina, R. M.
From Zhurnal Analiticheskoi Khimii (1965), 20(6), 739-42. Language: Russian, Database: CAPLUS
Glycerol is detd. directly by gas chromatography on acetylated dextrin on diatomite brick, with He as carrier gas. The
error is ∼2%.
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301. Dinitroglycerin and its derived products

By Desseigne, Gerard
From Mem. Poudres (1965), 45, 103-14. Language: French, Database: CAPLUS
Partial nitration of glycerin was studied with HNO3 alone or with mixts. of HNO3, H2SO4, and H2O (with or without
CH2Cl2). Better results were obtained with 97% HNO3. Thus, in a 750-ml. Keller flask contg. 50 g. 83% HNO3 cooled to
0° was introduced in 30 min. simultaneously with good stirring 92 g. pure glycerin and 362 g. 97% HNO3 cooled to 5°.
The temp. was kept <5° 30 min., the mixt. poured on 400 g. ice, and the homogeneous soln. neutralized with 2.16 moles
solid Na2CO3 at <20°, until pH was 8.0. The upper org. layer was decanted, NaNO3 filtered off, and the aq. layer extd.
with CHCl3, 200 ml. CHCl3 ext. and org. layer distd. in vacuo at <50° (flask temp.), and the residue washed with 50 ml.
2% Na2CO3 soln. and dried in vacuo or over CaCl2 to const. wt. In this way 165 g. nitric esters mixts. were prepd. in
89.5% yield. Chlorinated and acetylated dinitroglycerin derivs. were prepd. Glycerol dinitrochlorohydrin was obtained by
nitration of glycerol α-chlorohydrin with a mixt. of HNO3, H2SO4, and H2O (49, 48.4, and 2.6% resp.). Glycerol
dinitroacetate was prepd. by mixing tech. 100 g. dinitroglycerin and 50 g. 98% AcCl with good stirring. Anal. results for
all compds. prepd. are given.
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302. Binding of pentachlorophenol by actomyosin

By Bowen, William J.; Martin, Harold L.; Jacobus, William E.
From Biochemistry (1965), 4(10), 1936-41. Language: English, Database: CAPLUS, DOI:10.1021/bi00886a005
A study has been made of the binding of pentachlorophenol (PCP) to actomyosin because it causes extensive shortening
of glycerol-treated muscle fibers without degradation as occurs when shortening is induced by ATP. The binding is
increased markedly by decreases of pH from 9 to 7 and by addn. of KCl, tetramethylammonium chloride, and MgCl2.
Actomyosin in homogenized glycerol-treated muscle binds about 120 moles of PCP/105 g. of protein, but as myosin B it
binds about 175 moles/105 g. Affinities are low (30-70) and the addn. of salts increases them. Acetylation of actomyosin
greatly reduces the amt. of PCP bound, which suggests that binding occurs on amino groups, probably of lysine and
arginine residues. Methylation supposedly decreases the net neg. charge of the protein and more PCP is bound.
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303. Aspalathin, a novel C-glycosylflavonoid from Aspalathus linearis

By Koeppen, B. H.; Roux, D. G.
From Tetrahedron Letters (1965), (39), 3497-603. Language: English, Database: CAPLUS, DOI:10.1016/S0040-
4039(01)89333-3
cf. CA 60, 15972a. Isolation from A. linearis gave aspalathin (I), C21H24O11, an amorphous polyphenolic compd.
converted by CH2N2 in MeOH to a cryst. nonaacetate (II), C39H42O20, m. 152-4°, and a non-cryst. pentamethyl ether (III),
C26H34O11. Alkali fusion of I gave 1,3,5-(HO)3C6H3 and 3,4-(HO)2C6H3CO2H. I refluxed 2 hrs. in aq. 2N HCl failed to
liberate any sugar, thus suggesting the presence of a C-glycosyl compd. Formation of a fluorescent chelate with AlCl3
and the bathochromic shift of the uv absorption max. at 290 mµ (alc.) to 308 mµ (75 millimoles AlCl3 in alc.) indicated
direct attachment of the CO group to the A ring, though the colorless nature and the uv spectrum of I precluded
conjugation of the B ring with the CO group. Evidence of the CO group was provided by the ir bands at 1695, 1710 cm.-1
in the spectra of III and II, resp. In the presence of sunlight an alc. soln. of I slowly produced 2,3-dihydroisoorientin,
suggesting a dihydro structure for I. III oxidized with NaIO4 resulted in uptake of 2 moles HIO4 per mole I with formation
of 1 mole HCO2H. NaBH4 reduction of the oxidized III and acid hydrolysis of the product liberated glycerol. The
hexopyranosyl residue in I was confirmed by detection of glucose and arabinose on FeCl3 oxidn. of I or III. The identity
of I as a C-glucopyranosyldihydrochalcone was supported by the N.M.R. signals of II at τ 2.92, 3.00, 5.28, 6.98, 7.50-
8.25 ppm. The up-field signal at 8.22 ppm., assigned to the C-2'' acetyl required the group to have equatorial orientation
and spectrum therefore supports the identification of I as a C-β-D-glucopyranosyl compd. Acetylation of III gave an
amorphous product, C34H42O15, N.M.R. spectrum confirming the presence of 5-MeO and 4 Ac groups, with signal at τ
6.94 ppm. indicating the presence of 2 equally shielded CH2 groups. II treated with (CH2CO)2NBr and BzO2 in CHCl3
gave the α-bromodihydrochalcone, C39H41BrO20, m. 185°, as confirmed by the absence of N.M.R. signals in the 7.0
ppm. region, the appearance of the 3 residual protons of the ethylenic group as an A2X system, the resonance of the
remaining proton at α-C as a triplet at 4.48 and of the β-methylene protons as a doublet at 6.30. Comparison of the
spectra of I and phloretin in C5H5N in the 6-7 ppm. region showed striking similarity in the pattern of the ethylenic
protons. The C-1'' proton of I at τ 4.30 (10) was particularly evident in C5H5N. The spectrum of I in Me2SO4 showed a
broad signal at τ -3.70, assigned to the 2'-OH proton H-bonded to the CO group. I methylated with the theoretical amt. of
Me2SO4 produced a tetramethyl ether, giving a pos. FeCl3 reaction and showing low field resonance at τ -4.00 due to H-
bonded phenolic OH. I, 3'-C-β-D-glucopyranosyl-3,4,2',4',6'-pentahydroxydihydrochalcone, appears to be the 1st known
example of a naturally occurring C-glycosyldihydrochalcone.
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304. Absorption and excretion of drugs. XX. Effect of guaiacol glycerol ether on urinary excretion of the
sulfamethylthiadiazole in man
By Naito, Shunichi; Nakahara, Chiaki
From Yakugaku Kenkyu (1965), 36(5), 168-71. Language: English, Database: CAPLUS
cf. CA 64, 14038h. Sulfamethylthiadiazole (SMTD) and a mixt. of SMTD and guaiacol glycerol ether (GGE) were given
to normal adult humans after fasting overnight. Urine samples were assayed for free and total SMTD. GGE interfered in
the rate of acetylation of SMTD and resulted in a marked decrease in the excretion of total SMTD.
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305. Synthesis and chemical properties of methyl 2,3,6-tri-O-benzoyl-4-deoxy-4-thiocyano-α-D-glucopyranoside

By Gero, S. D.
4039(01)99936-8
Treatment of the readily available D-galactopyranoside (I) with KCNS at 140° 22 hrs. gave 47% D-glucopyranoside (II, R
= Bz, R' = SCN) (III), m. 194.0-4.5°, [α]29 D 60.3° (c 0.53, CHCl3). Desulfurization with Raney Ni followed by
debenzoylation and reacetylation of the product gave 78% Me 2,3,6-tri-O-acetyl-4-deoxy-α-D-xylo-hexopyranoside (II, R
= Ac, R' = H), m. 75-6°, [α]30 D 138° (c 0.5, CHCl3). The N.M.R. spectrum of III was completely consistent with the D-
gluco configuration with the C-1 conformation. NaOMe treatment of III gave the sodio deriv. of Me 4-deoxy-4-thio-α-D-
glucopyranoside, a key intermediate for the prepn. of the S-contg. analogs of maltose, cellobiose, and lactose. The
presence of the isothiocyanate I(R = Bz, R' = NCS) was expected either in the isolated III or in the mother liquor. For
comparative study by ir and N.M.R. spectroscopy 1,2-O-isopropylidene-3-O-ptolylsulfonylglycerol was treated with KCNS
in HCONMe2 to give the glycerol deriv. (IV), b0.02 51-3°, n19 D 1.4761. Chem. shift data and ir absorption spectra showed
lack of isothiocyanate. Debenzoylation of III with NaOMe (N atm.) and acetylation of the sirup with Ac2O-C5H5N gave the
D-glucopyranoside (II, R = Ac, R' = SAc), b0.005 145-8°, [α]29 D 128° (c 0.72, CHCl3), τ 1.97, 2.03, 2.07, 2.30 ppm., ν 763
cm.-1, indicating retention of the D-gluco configuration during alk. hydrolysis and reacetylation.
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306. Some refinements in the technique of pollen and spore extraction from soil
By Smith, Richard Thornton
From Laboratory Practice (1966), 15(10), 1120-3. Language: English, Database: CAPLUS
The following technique was developed esp. for silty soils contg. a large clay fraction. Dry the soil samples at 90-105°
overnight as soon as possible after sampling; but if the samples are raw humus or peat, then keep them cool and moist.
Crush the dried samples gently in a mortar and pass through a British Standard sieve of 22 mesh (800-µ apertures).
Weigh 0.5-5.0 g. soil into a 100-ml. conical flask, add 20 ml. of 10% NaOH, and simmer on a hot plate for 15 min. taking
care to keep the NaOH concn. more or less const. by the addn. of H2O. Decant through a 72-mesh nylon sifting cloth
(200-µ apertures), stir the filtrate, and decant again, but this time through a 122-mesh cloth (115-µ apertures) and into
250-ml. centrifuge buckets. Dilute with distd. H2O, stir, and then centrifuge for 15 sec. at 1800 rpm. Discard the
supernatant and repeat the centrifugation 2 or 3 times more for 15 sec. at 1400 and 1000 rpm. If there is a very high clay
content, then use Na hexametaphosphate (0.5 g./l. soln.) for the final wash. Transfer the residue with a small amt. of
H2O to a 30-ml. Ni crucible and 3/4 fill with 40% HF. Stir well and boil for 10 min. in a fume cupboard. Centrifuge in
plastic tubes and discard the supernatant. Add about 10 ml. of 15% HCl and transfer to 15-ml. glass tubes and heat in a
boiling water bath for 1 min., then centrifuge while hot. Repeat this stage and then wash the residue 3 times with distd.
H2O. Dehydrate the residues with 5 ml. AcOH, centrifuge, and discard the supernatant. Add 5 ml. of freshly prepd.
acetylation reagent (Ac2O-H2SO4 (9:1)), bring to a boil, and leave about 15 min. until a brown color develops, centrifuge,
and decant. Add 5 ml. AcOH, shake, centrifuge, and decant, and then wash with H2O. Add about 5 ml. 10% NaOH to
the residue and boil gently for about 10 min. Centrigue and decant, wash thoroughly with H2O, centrifuge, and decant.
Depending on likely pollen frequency and clarity, make up the ext. to a max. of 5 ml. with 1:1 glycerol-H2O to which 0.5%
water-sol. safranine has been added in the ratio of 1:50.
~0 Citings
307. Polyesterification of citric acid. I

By Jarusek, Jaroslav
From Chemicky Prumysl (1966), 16(11), 671-4. Language: Czech, Database: CAPLUS
The thermal degradation of citric acid (I) was investigated to det. its potential use in the manuf. of polyesters. I was
heated at 160, 180, and 200° resp., and the amts. of decompn. products (aconitic, itaconic, citraconic, and mesaconic
acids) were detd. at hourly intervals by polarography and paper chromatography. Decompn. at 160° is slow. At higher
temps., the decompn. rate rises rapidly. Esterification of the CO2H groups increases the stability of I considerably.
Perfectly neutral tri-Bu citrate (II) did not yield any decompn. products after 8 hrs. at 180°; only small amts. were found
after 2 hrs. at 200°. The stability of II is somewhat reduced by the presence of free acid, and sharply reduced if its OH
group is acetylated. The kinetics of the polyesterification of I with diethylene glycol at 160° are similar to those of the
reaction between succinic acid and glycerol; the conversion averages 75%. The resulting polyesters are colorless. I can
therefore be used in the prepn. of polyesters provided the temp. does not exceed 160°.
~3 Citings
308. Poly(oxymethylene) molding compositions

Esters of polyols were added to poly(oxymethylene) (I) to improve the impact strength, processability, and thermal
stability. For example, 1000 parts powd. I diacetate was mixed with 10 parts polyamide powder and 2 parts 1,1-bis(3-
tert-butyl-4-hydroxy-6-methylphenyl)butane. This mixt. (50 parts) was mixed with 50 parts glycerol triacetate (II) to form a
paste, and sufficient I was added in a drum mixer to obtain a mixt. contg. 5% II. The mixt. was pressure molded at
ambient temp., and the sheets obtained were ground, dried, extruded, and cut to give a granulate. Mech. properties of
the above mixt. were compared with the properties of I contg. no additives and of I contg. 5% glycerol.
~0 Citings
309. Oligomeric degradation phenols of pine lignin

By Nimz, Horst
From Chemische Berichte (1966), 99(8), 2638-51. Language: German, Database: CAPLUS
The isolation and structure elucidation is described of 2 diastereometric I (R = H) and the tetrameric II obtained by mild
hydrolysis of pine lignin. I and II show 2 bond types present in lignin, glycerol β-aryl ether bonds and diarylpropane
linkages; the latter were also demonstrated for the 1st time among the dehydrogenation products of coniferyl alc. (III).
The Rf values on silica gel thin-layer plates were detd. with the following solvent systems: 9:2 xylene-HCONMe2 (A),
25:25:1 xylene-EtOAc-HCONH2 (B), 1:1 C6H6-Me2CO (C), 1:2 C6H6-Me2CO (D), 3:1 C6H6-Me2CO (E), 5:1 C6H6-Me2CO
(F), 1:1 cyclohexane-EtOAc (G), and 5:2 cyclohexane-EtOAc (H). Pine (Picea excelsa) sawdust (3 kg.) was extd.
several days with 9:1 Me2CO-H2O, air-dried, ground, sieved (400 mesh/cm.2), percolated 3 days with 9:1 Me2CO-H2O
and 2 days with H2O, the residue percolated 10 days with H2O at 100° the hot ext. concd. to 2 l., and stirred slowly into 2
l. Me2CO, the pptd. sirup repptd. from H2O with Me2CO, and the residue from the combined aq. Me2CO solns. dissolved
in 1 l. 9:l H2O-Me2CO and treated slowly with stirring with 2 l. Me2CO to give 105 g. viscous, dark-brown sirup; a 50-g.
portion subjected to a 200-transfer counter-current distribution yielded 5.9 g. crude I (R = H) and 4.3 g. crude II. The
crude I (R = H) chromatographed on polyamide yielded 589 mg. amorphous I (isomer A) (IA), m. 100-17°, Rf 0.027 (A),
0.02 (B), 0.28 (C), and 558 mg. amorphous I (isomer B (IB), m. 94-115°, Rf same as IA. IA (100 mg.) treated 20 hrs. with
C5H5N-Ac2O yielded 105 mg. amorphous hexaacetate, m. 52-70°, Rf 0.34 (G), 0.43 (F). IB (100 mg.) yielded similarly
117 mg. amorphous hexaacetate, identical in Rf values to the product from IA. IA (100 mg.) and 100 mg. 2,4-
(O2N)2C6H3F in 2 cc. HCONMe2 shaken 15 hrs. at 20° with 70 mg. NaHCO3 and chromatographed on silica gel yielded
92 mg. pale-yellow, amorphous bis(2,4-dinitrophenyl) ether (IV) of IA, m. 109-18°, Rf 0.51 (C). IB (100 mg.) gave
similarly 105 mg. pale-yellow, amorphous bis(2,4-dinitrophenyl) ether (V) of IB, m. 114-20°, Rf same as IV. IV (35 mg.)
treated 20 hrs. with 1 cc. Ac2O and 1 cc. C5H5N yielded 37 mg. tetraacetate, pale-yellow, amorphous powder, m. 94-
105°, Rf 0.59 (F). V (40 mg.) gave similarly 45 mg. amorphous tetraacetate, m. 91-100° Rf 0.59 (F). Guaiacylglycerol β-
dihydroconiferyl ether (VI) (200 mg.) and 400 mg. Na2S.9H2O in 5 cc. 2N NaOH heated 14 hrs. under N at 135° in a
sealed tube gave 51 mg. dihydro deriv. (VII) or III, m. 63° Rf 0.39 (A), 0.26 (B), 0.38 (E). VI (500 mg.) in 5 cc. 2N NaOH
heated 14 hrs. at 135° under N, and the product hydrogenated in EtOAc over 50 mg. PtO2 during 1 hr. at 20° and 1 atm.
yielded 36 mg. VII and 216 mg. VIII, a sirup, Rf 0.42 (A), 0.64 (B), which, upon acetylation with C5H5N-Ac2O, yielded 230
mg. diacetate of VIII, sirup, Rf 0.22 (H). Veratrylglycerol β-dihydroconiferyl ether (IX) (240 mg.) and 5 cc. 2N NaOH
heated 2 hrs. under N at 170° gave 70 mg. VII and 22 mg. unreacted IX. IA or IB treated with aq. NaOH and Na2S
yielded 46% [4,3-HO(MeO)C6H3CH:]2 (X), m. 211-12° (3:1 cyclohexane-Me2CO). IA or IB (500 mg.) in 5 cc. 2N NaOH
heated 14 hrs. at 135° under N, and the product hydrogenated 3 hrs. in EtOAc over 50 mg. PtO2 at 25° and 1 atm.
yielded 41 mg. sirupy racemate mixt. of 1,2-diguaiacyl-1,3-propanediol, Rf 0.09 (A), 0.035 and 0.04 (B) (which from H2O
gave 11 mg. solid, m. 143.5°, Rf 0.035 (B), and 156 mg. racemate mixt. of XI, Rf 0.13 (A), 0.06 and 0.07 (B). XI gave
92% tetraacetate, glass, Rf 0.42 (VIII). IA or IB (100 mg.) in 1 cc. MeOH with 2 cc. CH2N2-dioxane during 2 days at 20°
yielded I (R = Me), Rf, 0.44 (C); the filtrate evapd., and the residue heated 2 hrs. at 170° with 5 cc. 2N NaOH in 1:1
dioxane-H2O yielded 23 mg. 4hydroxy-3,3',4'-trimethoxystilbene (XII). The crude II chromatographed on polyamide, and
the resulting amorphous powder (1.05 g.) subjected to a 200-transfer countercurrent distribution yielded II, m. 104-12°. II
(100 mg.) with C5H5N-Ac2O yielded 118 mg. octaacetate, m. 73-8°, RF 0.20 (G) and 0.34 (F). II (100 mg.), 75 mg. 2,4-
(O2N)2C6H3F, 50 mg. NaHCO3, and 2 cc. HCONMe2 shaken 20 hrs. at 20° yielded 95 mg. pale-yellow, amorphous
bis(2,4-dinitrophenyl)ether (XIII) of II, m. 116-28°, Rf 0.35 (F). XIII (52 mg.) with 2 cc. 1:l Ac2O-C5H5N at 20° during 20
hrs. gave 61 mg. hexaacetate, a pale-yellow, amorphous powder, m. 98-114°, Rf 0.44 (F). II (100 mg.) with NaOH and
Na2S yielded 17 mg. X. II (200 mg.) in 5 cc. 2N NaOH heated 14 hrs. under N at 135° and the crude product
hydrogenated in EtOAc over 50 mg. PtO2 yielded 45 mg. XIV, Rf 0.035 (A), 0.02 (B), 0.22 (C), which with Ac2O-C5H5N
yielded 0.28 g. hexaacetate, m. 65-75°, Rf 0.28 (G). XIII (100 mg.) in 1 cc. MeOH treated 2 days at 20° with 2 cc.
CH2N2-dioxane and the resulting di-Me ether, Rf 0.14 (F), 0.34 (D), heated 2 hrs. at 170° with 5 cc. 2N NaOH in 1:1
dioxane-H2O gave 12 mg. XII, m. 133° (7:2 cyclohexane-AcOEt). X (545 mg.) m. 212° 0.23 cc. Me2SO4, and 10 cc.
PhMe treated dropwise with stirring at 40° during about 20 min. with 1.1 cc. 2N NaOH, stirred 2 hrs. at 40°, and acidified
with 2N H2SO4 yielded 275 mg. XII, m. 133° (EtOH), Rf 0.62 (A), 0.82 (B), 0.80 (E).
~2 Citings
310. Liquid adhesive compositions having prolonged tackiness

By Pereny, Louis; Pereny, Evelyn K.; Gibbs, Eric G.; Pyron, Charles O.
CAPLUS
Low tack-pressure sensitive adhesives, having preferential adhesion to human skin and other surfaces, can be used for
repeated adhering and removal of articles from surfaces, without disrupting the compn. The adhesives may be applied to
the skin of a patient about to undergo surgery, after which a sterile drape of paper or plastic is positioned and adhered,
and possibly repositioned and readhered, to form a sterile field in the operation area, as disclosed in the main patent.
The compns. consist of an adhesive component of prolonged tackiness including a definite plasticizer; a film-forming
component; a solvent or mixt. of solvents to control drying time; and, for surgical use, a bacteriostatic and (or)
bactericidal agent. Suitable film-forming components include vinyl polymers and copolymers, cellulose acetate butyrate,
and Et cellulose. Suitable adhesion-producing components include polyacrylates and polymethacrylates, glycerol
phthalate, abietic acid-glycerol esters, amine-aldehyde and maleic anhydride resins. Suitable plasticizers include Bu
phthalyl Bu glycolate, acetylated castor oil, tricresyl phosphate and o- and p-sulfonamides. Suitable bacteriostats include
maleic anhydride (which may be included in the adhesive component), cresols, and chlorinated and thiochlorinated
phenols. Suitable volatile solvents include ≥ 1 org. esters, ketones, org. ether and oxide, arom. hydrocarbons, and
chlorinated aliph. hydrocarbons. The solvent component is chosen to produce the desired drying rate, viscosity, ease of
storage and min. traumatic effects on the skin. The various components are proportioned, correlated, and combined in
the adhesive film to provide controlled, limited but prolonged tackiness; also to provide that the cohesive or film tensile
strength and the adhesiveness of the film applied to the 1st surface substantially exceeds the tackiness of the film after
solvent removal, so that the adhesive film will adhere preferentially to the first applied surface and will resist film
disruption on repeated removal of the other surface (paper, cloth, film, etc.). For surgical applications the various
components and solvents should have a low irritating effect on the human skin. A typical compn. consists of a vinyl
chloride-acetate resin 8, a maleic anhydride-modified glycerol-abietic acid resin (Amberlac D-96) 3, an epoxidized oil-
type plasticizer (Paraplex G-50) 4, a Bu phthalyl Bu glycolate plasticizer (Santicizer B-16) 4, EtOAc 36, Me2CO 40, and
iso-BuCOMe 5 parts by wt. The vinyl film former with the plasticizers incorporated therein is added slowly to the solvent
mixt. until dissolved. Then the adhesion-promoting resin Amberlac D-96 is added and mixed until dissolved. After
filtration the compn. may be packed into aerosol spray containers at ∼0°F. or otherwise packaged.
~0 Citings
311. Isolation of sissotrin, a new isoflavone glycoside from the leaves of Dalbergia sissoo
By Banerji, A.; Murti, V. V. S.; Seshadri, T. R.
From Indian Journal of Chemistry (1966), 4(2), 70-2. Language: English, Database: CAPLUS
Air-dried and coarsely powd. leaves of D. sissoo (1 kg.) was extd. with 95% boiling EtOH (15 hrs. each time). The
combined ext. was concd. and the residual ext. extd. with petroleum ether and ether. Treatment of the remaining aq.
soln. with basic and neutral lead acetates, decompn. of the Pb salts and working up of the fractions did not yield any
cryst. product. The 2 fractions were mixed and refluxed 2 hrs. with H2SO4 (over-all concn. 7%), and the aq. soln. extd.
with ether (the ether ext. yielded a small amount of aglycon) and passed through a column of neutral Al2O3. Elution of
the column with C6H6 and with EtOAc to remove colored impurities and elution with EtOAc yielded 100 mg. sissotrin (I),
m. 212-14° (EtOH) (purple ferric reaction); [α]27 -53° [c 1.223, tetrahydrofuran (THF)] and -35.5° (c 1.35, HCONMe2); Rf
0.86 (30% HOAc, 17°); 0.92 (BuOH-HOAc-H2O, 4:1:5, upper layer, 24°); 1.0 (6 % HOAc, 17°); 0.0 (H2O); λMeOH max 262
mµ (log ε 4.38) and 325 mµ (log ε 3.70, inflexion); λMeOH-NaOAc max 263 mµ; λMeOH-AlCl3max 3273 mµ Redn. of I with Na-
Hg in alc. followed by acidification gave pink color. I gave an acetate (II) (Ac2O-C5H5N), m. 198-9° (MeOH). Attempts to
methylate I in THF with CH2N2 gave a low melting Me ether (III) (neg. ferric reaction). Acetylation of III (Ac2OC5H5N)
gave an acetate, which also could not be crystd. Most of I was recovered upon attempted hydrolysis of I in THF with 4%
H2SO4 2 hrs. on a steam bath; a small amount of biochanin A, m. 207-9° was obtained from the mother liquor. The aq.
filtrate showed the presence of glucose by paper chromatography. I (80 mg.) was refluxed 6 hrs. with 3 ml. PhOH and 4
ml. HI (d. 1.7). Working up of the reaction mixt. yielded genistein, m.p. and mixed m.p. 298-300°. On alk. hydrolysis of III
(2 hr. heating on a steam bath with 20% NaOH), HCO2H was detected in the products, which again confirmed the
isoflavone nature of the substance with the 2-position unsubstituted. KMnO4 oxidn. of III gave anisic acid (identified by
paper chromatography). On periodate oxidn. of I or II, glycerol was detected by paper chromatography. Thus, sissotrin
was identified as the 7-glucoside of biochanin A.
~3 Citings

312. Individual molecular species of phospholipids. III. Molecular species of ox-brain lecithins
By Renkonen, Ossi
From Biochimica et Biophysica Acta, Lipids and Lipid Metabolism (1966), 125(2), 288-309. Language: English,
Database: CAPLUS, DOI:10.1016/0005-2760(66)90070-1
cf. CA 63, 3295c. A mixt. of native choline plasmalogens and alkoxy lecithins was isolated from ox brain by partial alk.
methanolysis of the total lecithin; the prepn. appeared to be free of phosphatidyl cholines. Hydrolysis of total ox-brain
lecithins with phospholipase from Clostridium welchii converted all 3 subclasses of the glycerylphosphorylcholine lipids
into diglycerides; these were subsequently acetylated. The resulting mixt. of diglyceride acetates was sepd. by
chromatography on kieselgel G into ordinary diglyceride acetates (95.2%), plasmalogenic diglyceride acetates (1.9%),
and corresponding alkoxy compds. (2.2%). Chromatography evidence and observations on partial hydrolysis with
pancreatic lipase proved that the fraction of the ordinary diglyceride acetates contained about 99% 1,2-diglyceride
acetates and about 1% 1,3-diglyceride acetates. Hydrolysis of the plasmalogenic diglyceride acetates and the alkoxy
analogs with pancreatic lipase suggested that their long-chain acyl ester groups were located on C-2, and the acetyl
group on C-3, of glycerol. All 3 subclasses of diglyceride acetates wre fractioned on AgNO3-contg. kieselgel G into 4
subfractions which contained 0, 1, 2, and "many" double bonds, resp., in their long fatty acid chains proper. Furthermore,
the dienoic subfractions of the type 1-oleoyl-2-oleoyl-3-acetate and 1-stearoyl-2-linoleyl-3-acetate could be sepd. from
each other. The plasmalogen diglyceride acetates appeared to form Ag complexes even though they had vinyl ether
double bonds. The fatty acid chains at the C-1 and C-2 positions in the 12 main subfractions of diglyceride acetates
were analyzed by gas-liquid chromatography. The compn. of the major mol. species could be predicted from the results
by assuming that the no. of doublebonds is const. within each subfraction. The ordinary 1,2-diglyceride acetates were
also subjected in intact form to gas-liquid chromatography, giving 3-4 fractions of different mol. sizes in each of the main
subfractions. All 3 subclasses of ox-brain lecithins, the phosphatidyl cholines, the plasmalogens, and the alkoxy
lecithins, appeared to consist of similar populations of mol. species. The partial hydrolysis of 5 different types of
diglyceride acetates with pancreatic lipase is described. The primary ester groups appeared to be cleaved faster than
the secondary ones in 1,2-diglyceride acetates as well as 1,3-diglyceride acetates, and also in the corresponding 2 types
of plasmalogen compds. having vinyl ether chains on C-1; even the alkoxy analogs of 1,2-diglyceride acetates were
deacetylated. 35 references.RCCF
~6 Citings
313. High molecular weight polyformaldehyde

By Kaufhold, Robert; Eifert, Werner
From Ger. (East) (1966), DD 50311 19660920, Language: German, Database: CAPLUS
The title polymer was obtained from a low mol. wt. polyformaldehyde (I) by depolymn., acetylation, and stabilization with
other polymers. Thus, 100 parts by wt. powd. I (reduced viscosity 0.23) prepd. from crude HCHO (98.5%) in the
presence of Et3N was heated with 400 parts by wt. paraffinic hydrocarbon mixt. (b. 180-250°) 65 min. at 125°. I had
20.45 wt. % wt. loss in the depolymerization. The suspension was treated with 100 parts Ac2O and 0.25 parts NaOAc
(onI). The acetylated I (reduced viscosity 0.58) was isolated, freed from catalyst and dried. The dried polymer was
mixed with 86% aq. EtOH 250, 1,4-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)butane 0.3, and a mixed polyamide 1.5
parts, the polyamide being composed of 38% ε-caprolactam, 35% hexamethylene adipate and hexamethylene sebacate.
The solvent was removed and the stabilized polymer dried at 110°/30 mm. Dried I had tensile strength (DIN 53,455) 702
kp./cm.2 and impact strength (DIN 53,453) 85 kp./cm.2 at 20°. The depolymn. was also carried out by heating in
ethylene glycol, glycerol, and glycol hemiacetal, and the resulting HCHO formed hemiacetals. Thus purified I had after
acetylation phys. properties similar to the above.
~0 Citings
314. Heteroside derivatives by fermentation

By Bellet, Paul; Gerard, Daniele
From Fr. (1966), FR 1455012 19661014, Language: French, Database: CAPLUS
Nutrient medium, 100 ml., contg. glycerol, corn steep liquor, soybean flour, malt ext., NaCl and CaCO3 was sown with a
10-ml. inoculum of Trichothecium roseum; 10 mg. digitoxide in 0.25 ml. HCONMe2 was added and mixt. incubated at 30°
for 168-92 hrs. Similar flasks were prepd. to give a thick beige culture, pH 6.5-7.5. The filtered mycelium was washed
with acetone, and washings were concd. in vacuo, extd. with CHCl3-MeOH (4:1) and the ext. was used along with
CHCl3-EtOH (2:1) to ext. the filtrate from the mycelium. Bulked exts. were dried, evapd. to dryness in vacuo, and
purified by paper chromatog. with iso-BuCOMe-iso-Pr2O-tetrahydrofuran (40:20:15) satd. with HCONH2 to give, with
Kedde's reagent, a new substance (I) Rf 0.10 (40%), insol in MeOH. I, 600 mg. was acetylated with 60 ml. anhyd.
C5H5N and 60 ml. Ac2O at 30° for 36 hrs., cooled, poured into water, extd. with CHCl3, ext. with N HCl, then water until
neutral, dried, and concd. in vacuo to give an oil, which was chromatographed on Al2O3, eluted successively with ether,
CHCl3, and CHCl3-MeOH (4:1), followed by chromatog. on Florisil to give 600 mg. acetylated product (II), sapon. no.
335. To deacetylate, II was dissolved in 30 ml. dry EtOH, 1 ml. N alc. potash added, the mixt. allowed to stand at
ambient temp. for 24 hrs., acidified with HCl to pH 4, 10 ml. water added, and the mixt. extd. with CHCl3. The ext. was
dried, evapd. to dryness in vacuo, the residue redissolved in CH2Cl2, and pptd. by adding Et2O and iso-Pr2O to give 400
mg. neodigitoxide 1, a white solid m. 160° (approx.), Rf 0.1, sapon. no. 51-4. Similarly, biol. conversion of digitoxide by
(1) Streptomyces erythraeus gave an acetylated product, which gave neodigitoxide 2 (III) on deacetylation, m. 191-3°, Rf
0.20; and (2) by Gongronella urceolifera gave a heteroside G1 and G2 mixt. (IV) which crystd. together in rectangular
platelets in a 1:8 proportion, m. 235° (approx.) (CHCl3/ether), solvated with 10-12% CHCl3. I-IV had appreciable physiol.
activity.
~0 Citings
315. Food spreads

A product with a low caloric value and properties similar to those of margarine was prepd. from a water-in-oil emulsion.
Milk was not used. The fat concn. was low (30-50%), and could be from butter, soybean, cottonseed, safrole, or maize
oils. Emulsifiers (0.25-1%) were added, e.g. partial glycerol esters of higher fatty acids, acetylated glycerol esters of
higher fatty acids, or partial polyglycerol esters of higher fatty acids. The water content was ∼35-66%, and contained the
water-sol. ingredients NaCl, Na benzoate, diNa-Ca EDTA, and propyleneglycol alginate. Thus, the water phase was
added slowly, with stirring, to the oil phase, which was the continuous phase. The emulsion was cooled at 8-12° to a soft
product that could be poured into plastic containers. Lecithin (0.1-0.2%) could be added for anti-spattering properties.
Flavoring, coloring substances, and vitamins were also added.
~0 Citings
316. Ether-containing lipids of dogfish (Squalus acanthias) liver

By Malins, D. C.
From Biochemical Journal (1966), 100(2), 31P. Language: English, Database: CAPLUS
cf. CA 62, 9502c. Diacyl glyceryl ethers (I) were sepd. from triglycerides on layers of silica gel in light petroleum (b.p. 60-
80°) (II)-Et2O (90:10, vol./vol.). The upper 20% of the I fraction was removed from the plate and dissolved in
dinitrophenylhydrazine (III) in HCl in 15 min. and chromatographed in Il-EtH2O (90:10, vol./vol.). A concentrate of more
polar neutral lipids contg. plasmalogenic diglycerides was chromatographed on a silica gel layer using II-Et2O (70:30
vol./vol.). The lipids were dissolved in HCl-III and chromatographed in II-Et2O (90:10, vol./vol.). The cleavage products
of plas-malogenic diglycerides and also a fraction contg. diglycerides, monacyl glyceryl ethers, and unidentified sterols
were eluted. This fraction was refluxed with Ac2O and chromatographed in II-Et2O (80:20, vol./vol.) yielding zones of
esterified sterols, acetylated diglycerides, and acetylated monoacyl glyceryl ethers. Acetyl derivs. of free glyceryl ethers
and monoglycerides were resolved under similar conditions. Aldehydes from phosphatide plasmalogens were liberated
as III derivs. The lipid content of the distal lobe of fish liver varied from 31 to 56%; the ranges of compn. were 15-48% I,
49-82% triglycerides, 1.0-2.2% phospholipids, 0.01-0.03% aldehydes of phosphatide plasmalogens, 0.05-0.23% neutral
plasmalogens, 0.02-0.06% plasmalogenic diglycerides, 0.01-0.02% nonesterified plasmalogens, 0.2-0.4% onoacyl
glycerol ethers, and 0.36 and 0.38% (2 specimens) diglycerides.
~0 Citings
317. Elastic foams

cf. CA 64, 19908e. Compds. having the formula (ROCOCH2)x, where R is a polyether or a polyester, optionally
branched, X is an Ac or nitrile group, and n is ≥2, are converted with HCHO and a conversion product of a polyamine and
CO2, (e.g. piperazinecarbamate), in the presence of 0.01-20.0% by wt. of an ortho ester of Ti or Zr or an Al. The free OH
groups of the polyester (from adipic or phthalic acid with a polyhydric alc.) or the polyether (from ethylene oxide,
tetrahydrofuran, etc., optionally in the presence of triols, such as glycerol) can be acetoacetylated or cyanoacetylated.
Addn. of a small amt. of silicone oil (surfactant) gave uniform foaming with definite pore d. The foamed product had fine
pores and good elasticity. Thus, to 40 parts polyester from adipic acid, diethylene glycol, and glycerol (OH no. 137.5),
the OH groups of which were acetoacetylated, 2 parts Al isobutylate was added with stirring. The mixt. was mixed with
0.8 part silicone oil (viscosity 5000 cp.), 1.2 part HOAc, 0.23 part piperazine and 7.59 parts of a 50% soln. of HCHO in
MeOH until a tough paste was obtained. After several min., a homogeneous foam with fine pores and a d. of 0.11 was
obtained.
~0 Citings
318. Determination of hydroxyl number in the presence of acid catalysts

By Yukhnovskii, G. L.; Prilutskaya, N. V.; Semova, V. I.
From Lakokrasochnye Materialy i Ikh Primenenie (1966), (3), 48-51. Language: Russian, Database: CAPLUS
The acetylation of OH groups with Ac2O was modified to avoid heating and prolonged reaction times. The acetylating
mixt. contained 17.5 g. Ac2O in 100 ml. EtOAc and HClO4, which is added in the form of a 5% soln. in EtOAc. The
sample is treated with 5 ml. acetylating mixt. at room temp., and the excess of Ac2O is then hydrolyzed with 2 ml. H2O
and 10 ml. of a pyridine-H2O mixt. The AcOH formed is retitrated with 0.5N alc. KOH in the presence of phenolphthalein.
Optimum concns. of HClO4 are 0.004-0.006 mole/l. (1 drop/100 ml.); the reaction is practically completed within 5 min.
The recommended duration of treatment is about 20 min. The results remain unchanged even after several hrs. Other
strong acids such as H2SO4 and H3PO4 are less convenient. Toluene, xylene, and hexane, which are sometimes
necessary for dissolving the sample, do not interfere with the detn. In the acetylating mixt., EtOAc may be replaced by
toluene or xylene. Glycerol and related compds. are less sol. in the acetylating mixt.; then it is recommended to increase
the concn. of HClO4 to 0.1-0.2 mole/l. The new method is reliable for detg. the OH concn, in OH-contg. amines, in oils,
polyols, glyptals, etc.
~0 Citings
319. Determination of alcoholic hydroxy group in organic compounds by the succinic anhydride method
By Narang, C.K.; Mathur, N.K.
From Indian Journal of Chemistry (1966), 4(6), 263-4. Language: English, Database: CAPLUS
Succinic anhydride-C5H5N reagent (CA 63, 10687g) was used for the detn. of alc. OH groups in org. compds. including
sugars. Thus, a sample contg. 2-3 meq. of the OH compd. was heated (steam-bath) with 5 mL. A for an appropriate time
(monohydric alc., 45-60 min.; glycols, glycerol, hydroxy acids, and sugars, 2 h.). The mixt. was dild. with 50 mL. H2O,
cooled, and titrated with 0.5N NaOH with phenolphthalein as indicator. The following compds. were estd. by this method:
MeOH, EtOH, iso-PrOH, BuOH, sec-BuOH, 2-methyl-1-propanol, 2-propen-1-ol, 3-methyl-1-butanol, 2-methyl-3-butanol,
1-hexanol, 1-octanol, 2-octanol, 1-hexa-decanol, cyclohexanol, 2-methylcyclohexanol, benzyl alc., 2-methoxyethanol,
diethylene glycol mono-Me ether, 2-propoxy-ethanol, menthol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, glycerol,
chloroethanol, borneol, glycollic acid, lactic acid, malic acid, tartaric acid, glucose, and sucrose. The special advantage
of this reagent is in the detn. of glycol ethers where the ether linkage is not hydrolyzed as in the acetylation method.
H2O, aldehydes, ketones, and ethers do not interfere; phenols, however, must be absent.
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320. Coating of selected foods with acetylated monoglycerides

By Luce, Gerald T.
From Papers presented at [the] Meeting - American Chemical Society, Division of Organic Coatings and Plastics
Chemistry (1966), 26(2), 97-106. Language: English, Database: CAPLUS
Acetylated monoglycerides consist of partial or complete esters of glycerol with a mixt. of HOAc and edible fat-forming
fatty acids. Partially acetylated monoglycerides made from fully hydrogenated fats have unusually stable α-cryst.
structure which enables them to be formed into thin, translucent films which are flexible in a temp. range of ∼ -30° to
+37°. The films are applied as protective coatings to foods by dipping, curtain coating, spraying, or panning. Coating
levels are controlled in the dip method by the temp. of the subject and of the coating, and immersion time. With curtain
or spray coating, the coating level is controlled by the temp. of the subject and of the coating, the nozzle size, pump
capacity, and conveyor speed. Acetylated monoglyceride film coatings are useful for protecting various foods from
oxidative rancidity, dehydration or abnormal hydration, and freezer burn. These coatings also are functional as release
and polishing agents.
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321. Altered fatty acid distribution of glycerophosphatides induced by acetolysis

By Renkonen, O.
From Lipids (1966), 1(2), 160-1. Language: English, Database: CAPLUS, DOI:10.1007/BF02533012
A rearrangement of fatty acids between positions 1 and 2 of the glycerol moiety of lecithin phosphatidylethanolamine,
and phosphatidylserine occurs during acetolysis. The mechanism of this alteration in fatty acid distribution is obscure,
but preliminary evidence indicates it is intramol. in nature. Acetolysis is not recommended for analytic
dephosphorylations. Phospholipase C followed by acetylation of the diglycerides is suggested for characterization of
individual mol. species of phospholipids.
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322. Surface-active chemicals as regulators of plant growth, membrane permeability, and resistance to freezing
By Kuiper, Pieter J. C.
From Mededelingen Landbouwhogeschool Wageningen (1967), (3), 23 pp.. Language: English, Database: CAPLUS
The effect of 2-alkenylsuccinic acids, alkyltrimethylammonium bromides, alkylimidazolines, and alkyl Me sulfoxides was
examd. on water permeability of bean roots and retardation of growth of young bean plants. In each type of compd., the
effectiveness increased with the increasing no. of C atoms in the hydrocarbon chain, viz. approx. 2-fold with addn. of
each CH2 group to the chain. The effective concn. range was narrow for the alkyl trimethylammonium bromides and
broad for the alkyl Me sulfoxides. Chain length did not increase the effective concn. range. The effect of decenylsuccinic
acid and its monoamides on growth retardation of beans depended on pH. At pH 4, the free acid was the most active
compd. At pH 6.5, the effectiveness of the compds. increased in the sequence amide, dimethylamide, hydrazide,
dimethylhydrazide. The same order was observed for stimulation of growth of excised cotyledons of Cucurbita ficifolia
and for induction of frost resistance in strawberry flowers. Survival of the flowers was, resp., 8% (control), 10%
(decenylsuccinic acid), 30% (decenyl-N,N-dimethylsuccinamic acid), and 40% (decenyl-N,N-dimethylsuccinic hydrazide).
When bean roots were exposed to acetylated glycerol, glucosepentaacetate, or sucrose octaacetate, water and
electrolyte permeability of the roots was increased. Effectiveness increased with the no. of acetyl groups in the mol.
Growth of beans and excised Cucurbita cotyledons was retarded by the acetylated compds. In a field test, 2 sprays with
10-2M glycerol triacetate on potato plants increased the fresh weight of foliage 19% and tuber yield 27%. 1,5-Difluoro-
2,4-dinitrobenzoate protected young bean plants against a freezing period of 8 hrs. at -3°. 1-Fluoro-2,4-dinitrobenzoate
was ineffective.
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323. Structure and abundance of rat tissue cardiolipins

By Courtade, Simon; Marinetti, Guido V.; Stotz, Elmer H.
Database: CAPLUS, DOI:10.1016/0005-2760(67)90015-X
Cardiolipins of rat tissues were isolated by column chromatog. and analyzed. The P content ranged 2.61-3.64%. The
ester:P ratio ranged 1.63-2.09, and the glycerol:P ratios 1.34-1.68. The fatty acid spectrum of the tissue cardiolipins
showed some, like heart, kidney, and liver, to be highly unsatd. and others, like brain, lung, and testis, to be highly satd.
Analysis of the fatty acids released by phospholipase A demonstrated that certain fatty acids are preferentially β-linked,
but on the whole, the fatty acid distribution is much more random than that of other phospholipids, like the lecithins. All
the rat tissue cardiolipins are degraded by hot HOAc to yield diglycerides, very small amts. of monoglycerides, and other
P-contg. products. However, only with rat liver cardiolipin, beef heart cardiolipin, and a synthetic cardiolipin are
appreciable amts. of water-sol. P released. On treatment with NaOMe at 0°, all rat tissue cardiolipins give rise to 4-6 lyso
derivs. resulting from the sequential loss of one or more fatty acids. All cardiolipins are eventually completely degraded
to fatty acid Me esters, a water-sol. P compd., and smaller amts. of other products including free fatty acids and vitamin
A. In the case of rat liver cardiolipin, alk. hydrolysis yields vitamin A but not in stoichiometric amt. All cardiolipins react
with acetic anhydride-14C to yield a radioactive acetylated deriv. Whereas beef heart cardiolipin has a structure
consistent with the recently synthesized cardiolipin, the cardiolipins of rat tissues are not consistent with this structure.
New provisional structures for the rat tissue cardiolipins are proposed in which one of the phosphate groups bears a 3rd
moiety (such as vitamin A) as a tertiary phosphate ester or the phosphate group bears a fatty acid as a mixed carboxylic
acid-phosphoric acid anhydride. 33 references.
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324. Stereoselective hydrolysis of racemic α-methyl-β-dihydroxyphenylalanine esters and derivatives

From Brit. (1967), GB 1069064 19670517, Language: English, Database: CAPLUS
An aq. nutrient medium contg. 0.5% Et lactate, 0.2% KH2PO, 0.2% (NH4)2SO4 and traces of MgSO4 and FeSO4, was
brought to pH 6 and sterile-filtered into 1-l. conical flasks in 50-ml. portions, to each of which was added 4 ml. 5% CaCO3
suspension (sterilized at 121° for 1 hr. in an autoclave). The mixt. was inoculated with a spore suspension of Penicillium
daleae (Do 120), incubated for 3 days at 28° in a circular shaker and 10 ml. 5% sterile-filtered DL-α-methyl-β-(3,4-
dimethoxyphenyl)alanine Et ester soln. added, followed by a similar incubation. The contents of the flask were bulked,
pH was adjusted to 4-5, mycelium sepd. by centrifuging, 20% NaOH added to pH 10, and the soln. extd. 3 times with
EtOAc. The org. phase, contg. residual alanine ester, was washed with water, dried over anhyd. Na2SO4, filtered, the
solvent distd. in vacuo, the residue treated with 10 ml. anhyd. pyridine and 10 ml. Ac2O in a sealed tube for 20 hrs. at 37°
and acetylating reagents were distd. in vacuo to give N-acetyl-α-methyl-β-(3,4-dimethoxyphenyl)alanine Et ester (23%,
28% pure), [α]22D 40.6. The aq. phase, contg. α-methyl-β-(3,4-dimethoxyphenyl)alanine (I), was neutralized with 17%
HCl, freeze-dried, the residue acetylated similarly, the suspension evapd. in vacuo, 40 ml. water added, the soln.
adjusted to pH 7, and filtered. The filtrate was adjusted to pH 2 with 17% HCl, extd. 3 times with EtOAc and the
combined org. phases were treated as above to give the N-acetyl deriv. of I, (26%, 68% pure), [α]22D -20.2. Similar
stereospecific hydrolyses occurred using 0.5% glycerol or glucose instead of Et lactate, varying the nutrient medium,
using DL-α-methyl-β-(3,4-dimethoxyphenyl)alanine Bu ester or fungi such as P. janthinellum, Mortierella rammamiana,
Cephalosporium ciferi, or Trichoderma viride.
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325. Specific nature of plant cell wall polysaccharides

By Nevins, Donald J.; English, Patricia D.; Albersheim, Peter
From Plant Physiology (1967), 42(7), 900-6. Language: English, Database: CAPLUS, DOI:10.1104/pp.42.7.900
The polysaccharide compns. of cell walls were detd. by quant. analysis of the sugars rhamnose, fucose, arabinose,
xylose, mannose, galactose, and glucose. Cell walls were hydrolyzed in 2N trifluoroacetic acid and the liberated sugars
reduced to their resp. alditols. The alditols were acetylated and the resulting alditol acetates were sepd. and quant. detd.
by gas chromatog. using myoinositol as an internal standard. Analysis were carried out using common bean (Phaseolus
vulgaris varieties Red Kidney, Pinto, and Small White), mung bean (P. aureus), soybean (Glycine max varieties Harosoy
and Harosoy 63), barley (Hordeum vulgare varieties Atlas and Atlas 46), and corn (Zea mays variety Golden Rocket).
For varieties within any 1 species the cell wall compns. were identical. There were differences between species and
between genera. The cell walls of the roots, hypocotyls, first internodes, and primary leaves of the common bean each
had a characteristic sugar compn. Sycamore (Acer pseudoplatanus) cells were grown in suspension culture in a
modified M-6 medium contg. one of the following C sources: sucrose, maltose, glucose, galactose, mannose, or glycerol.
The sugar compn. of the cell walls varied according to the C source. Although the sugar compn. of the cell walls appears
to be genetically detd., the compn. can be altered by nongenetic conditions.
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326. Mannose-containing oligosaccharides isolated from α1-acid glycoprotein of human plasma
By Sato, Tokutaro; Yosizawa, Zensaku; Kotoku, Toshimitsu; Masubuchi, Masaaki
CAPLUS, DOI:10.1016/0006-291X(67)90264-1
The hydrazinolyzate of the α1-acid glycoprotein of human plasma was oxidized with Na metaperiodate and subsequently
reduced with NaBH4. After N-acetylation of the acid hydrolyzate of the reduced product, mannose-contg.
oligosaccharides, oligs I, II, and III, were isolated. Paper chromatog. sepd. olig I into olig I-a and olig I-b. The mannose
residue in olig I-a was substituted at C3 with N-acetylglucosamine. The N-acetylglucosamine residue in olig I-b was
present at the nonreducing end and was linked to C3 of the mannose residue. Olig I-b consisted of olig I-a and glycerol.
Dextrorotation of olig I-b suggested the α-anomeric configuration of the mannosyl linkage. Levorotation of olig I-a
suggested the β-anomeric linkage. Oligs II and III contained hexose and glucosamine. Oligs I-a and I-b were
characterized as O-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1 → 3)-D-mannose and O-(2-acetamido-2-deoxy-β-D-
glucopyranosyl)-(1 → 3)-O-α-D-mannopyranosyl-(1 → 2)-glycerol, resp.
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327. Isolation of guaiacylglycerol and its dimeric β-aryl ether from spruce lignin
By Nimz, Horst
From Chemische Berichte (1967), 100(1), 181-6. Language: German, Database: CAPLUS
The DL-threo- (I) and DL-erythro-4,3-HO(MeO)C6H3CH(OH)CH(OH)CH2OH (II) were isolated from spruce lignin which
contained predominantly I. The sepn. of the 2 diastereomeric forms was achieved by the fractional crystn. of their
tetraacetates. An addnl. degradation phenol of the spruce lignin is the guaiacylglycerol β-guaiacylglycerol ether IIIa (R =
OH, Q = CH2OH) (III) whose isolation and structure detn. is described. The Rf values of the various compds. were detd.
with the following solvent systems: 9:2 xylene-HCONMe2 (A) 25:25:1 xylene-AcEt-HCONH2 (B), 1:1 C6H6-Me2CO (C)
(on silica gel), 1:1 cyclohexane-AcOEt (D) (on silica gel), 9:1 cyclohexane-AcOEt (E) (on silica gel), and 6:1 C6H6-EtOH
(F) (on polyamide powder). Spruce wood (Picea excelsa) (3 kg.) percolated with H2O at 100°, the ext. dild. with Me2CO,
the pptd. hemicelluloses filtered off, the filtrate subjected to a counter-current distribution and fraction D evapd., and the
brown sirupy residue (3.75 g.) chromatographed on polyamide powder gave 310 mg. I-II mixt. which dissolved in AcOEt,
satd. with H2O, and kept at room temp. deposited 30 mg. I-II, m. 123-5°, Rf 0.06 (A), 0.28 (C), 0.40 (F). Crude I-II mixt.
(240 mg.) treated with C5H5N-Ac2O, and the product chromatographed on silica gel gave 280 mg. acetate (IV) of I-II,
sirup, Rf 0.65 (D), which dissolved in about 15 cc. AcOEt-petroleum ether and kept several weeks deposited 180 mg.
tetraacetate of I, m. 83-5°. Fraction E of the counter-current distribution evapd., and the residue (2.95 g.)
chromatographed on polyamide powder yielded 390 mg. hygroscopic III, Rf 0.013 (A), 0.31 (F). III (85 mg.) treated with
Ac2O-C5H5N and chromatographed on silica gel gave 102 mg. hexaacetate of III, glass, Rf 0.36 (D); it softens to a sirup
above 30°. III (70 mg.) in 2 cc. HCONMe2 shaken 15 hrs. at 22° with 50 mg. 2,4-(O2N)2C6H3F and 40 mg. NaHCO3,
filtered, concd., and treated 20 hrs. with 2 cc. each C5H5N and Ac2O gave 98 mg. dinitrophenyl ether of III, yellow,
amorphous powder, m. 63-80°, Rf 0.45 (D). III (400 mg.) in 10 cc. 2N NaOH heated 14 hrs. in a sealed tube under N at
120°, cooled, acidified with 2N H2SO4, and extd. with AcOEt, and the dried ext. hydrogenated 4 hrs. over 50 mg. PtO2
yielded 4,3-HO(MeO)C6H3Et (V), Rf 0.76 (A), 0.89 (B), 130 mg. VI, Rf 0.105 (A), 0.033 (B), and 0.52 (C), and 31 mg. I-II
mixt. The V from 400 mg. III treated with 75 mg. 2,4-(O2N)2C6H3F, and the crude product chromatographed on silica
gel gave 25 mg. 2,4-dinitrophenyl ether of V, pale yellow, m. 86° (MeOH). IIIa (R = Q = H) (130 mg.) treated with
C5H5N-Ac2O gave the tetraacetate, sirup, Rf 0.55 (D). I-II mixt. (31 mg.) obtained by the alk. degradation of 400 mg. III
acetylated and chromatographed on silica gel gave 24 mg. sirupy tetraacetate which dissolved in AcOEt-petroleum ether
and seeded, deposited 16 mg. tetraacetate of I, m. 102-6°, 112-14° (after 2 recrystns.); the mother liquor gave 2 mg.
crude tetraacetate of II, m. 81-95°.
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328. Diol lipids. V. Microacetylation of diols and triols for gas-chromatographic analysis
By Vaver, V. A.; Dorogov, V. V.; Bergel'son, L. D.
From Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1967), (12), 2681-4. Language: Russian, Database:
CAPLUS
Evapg. 1 ml. MeOH soln. of 2.27 mg. 2,3-butanediol, 2.26 mg. (CH2OH)2, 1.1 mg. 1,2-propanediol and 7.25 mg. glycerol
in vacuo at 50° and heating the residue 1 hr. with 0.9 ml. 2:1 AcOH-AC2O, with a trace of 72% HClO4 gave, after addn.
of abs. MeOH and heating 15 min. at 30°, followed by distn. with C6H6, a soln. of polyol acetates which was examd.
chromatographically and contained 32.3% 2,3-butanediol acetate, 31.4% ethylene glycol acetate, 47.6% 1,3-propanediol
acetate, and 74% glycerol acetate if the mixt during the acetylation was kept 1 hr. at 120°; at 50°, the values were 54.5,
51.2, 73.2, and 85%, resp. If acetylation is run with Ac2O in EtOAc contg. HClO4, the yields are 90, 100, 100 and 81.2%
after 1 hr. at 30° and the residual AcOH is removed by sorption on Al2O3 instead of distn. [J. S. Fritz and G. H. Schenk
(1959)]. The above method is readily applicable to detn. of diols in neutral lipids of plants and bacteria as well as in
phospholipids of animals.
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329. Diol lipids. Dihydric alcohols in the phospholipids of mammalian tissues

By Vaver, V. A.; Shchennikov, V. A.; Bergel'son, L. D.
From Biokhimiya (Moscow) (1967), 32(5), 1027-31. Language: Russian, Database: CAPLUS
Homogenized rat liver and cattle heart were extd. with a CHCl3-MeOH mixt., the cephalin fraction isolated by column
chromatog., subjected to acetolysis, the acetates of diglycerides sepd. therefrom by methanolysis and thin-layer
chromatog. on silica gel, the starting zone eluted by MeOH, acetylated, and fractionated by gasliquid chromatog. It was
found that the liver lipids contained 2 parts of 1,3-propanediol and the heart lipids 3 parts of ethylene glycol, 3 parts of
1,3-propanediol, and traces of 1,3-butane diol per 100 parts of glycerol. Analogous chem. procedures applied to mixts.
of lipids devoid of diols did not yield any diols, while the procedure destroyed any added free diols, an indication that they
are present in the organs in bound form. 13 references.
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330. Cashew oils. II. Derivatives of the main components of cashew nut shell oil
By Kaufmann, Hans P.; Barve, J.
From Fette, Seifen, Anstrichmittel (1967), 69(8), 577-82. Language: German, Database: CAPLUS
The prepn. and properties of derivs. of 2-carboxy-3-pentadecylphenol (I) and 3-pentadecylphenol (II) are described.
Acetylated I 1.6, 1,2-O-isopropylidene glycerol 1.6, and p-toluenesulfonic acid 0.1 g. was dissolved in 100 ml. C6H6 and
heated with 3 g. dry MgSO4. The mixt. was washed with water, then with cold 50% Na2CO3, and finally with water.
Isopropylideneglycerol ester of I, m. 49.5°, was obtained in 10% yield as a waxy solid after drying and chromatographic
purification of the crude product. II (1.5 g.) in 30 ml. toluene was treated with 3 g. NaOH in 18 ml. water. Purified COCl2
was bubbled through the soln. at 30-5°, after which the mixt. was heated to 100°, washed with water, and dried over
CaCl2; the solvent was evapd. II carbonate, m. 44.5°, was obtained. Esters of II were prepd. by treating cold II in a mixt.
of C6H6 and pyridine with the acid chloride. M.p. and percentage yields are given for the II esters of stearic 50°, 94;
palmitic 46.5°, 75.9; myristic 43.5°, 93.1; lauric 34°, 72; oleic (liq.) 59; linoleic acid (liq.), 47%.
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331. Acetylated peptide chains in bullfrog hemoglobins

By De Witt W; Ingram V M
From Biochemical and biophysical research communications (1967), 27(2), 236-41, Language: English, Database:
MEDLINE
~1 Citing
Copyright © 2018 U.S. National Library of Medicine.
332. Two-dimensional-reaction thin-layer chromatography in the analysis of mixtures of alkenylacyl, alkylacyl,

and diacyl choline phosphatides
By Viswanathan, Chittur V.; Phillips, Frederick C.; Lundberg, Walter O.
From Journal of Chromatography (1968), 38(2), 267-73. Language: English, Database: CAPLUS, DOI:10.1016/0021-
9673(68)85038-1
Alkenylacyl, alkylacyl, and diacyl choline phosphatides from beef heart were converted quant. to the corresponding
diglyceride acetates by enzymic cleavage with phospholipase C followed by acetylation with pyridine and Ac2O,
according to O. Renkonen (1965). The diglyceride acetates were analyzed by a 2-dimensional-reaction thin-layer
chromatographic procedure which permitted a quant. detn. of the 3 analogs, the corresponding fatty acid compns., and
the fatty acid compns. of the alkenylacyl analog. The diglyceride acetates in CHCl3 were spotted on silica gel G plates,
then developed with Skelly F-Et2O (88:12). After drying, the spots were detected by spraying with 5% iodine in CHCl3.
Unsprayed spots are sprayed then with 2N NaOMe in MeOH to interesterify the fatty acid esters of alkylacyl glyceryl
acetates, diacyl glyceryl acetates, and 2-acyl-3-acetyl glycerol. After drying, the plate was developed in the 2nd
dimension with PhMe. Reference spots were sprayed with 5% iodine in CHCl3. Aldehyde spots from the 1st
development and Me ester spots from the 2nd development were analyzed by gas chromatog. according to C. V.
Viswanathan (1968). Fatty acid compns. obtained by the 2 methods are presented and exhibit good agreement. An
unknown compd. was observed which was identified tentatively as dialkyl glyceryl acetate.
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333. Triglyceride fraction of Helleborus abchasicus oil

By Dalakishvili, Ts. M.; Kemertelidze, E. P.
From Khimiya Prirodnykh Soedinenii (1968), 4(5), 312-13. Language: Russian, Database: CAPLUS
From the subterranean portion of the title plant a fatty oil was isolated. The oil was isolated and then sepd. on a silica gel
column with Et2O-hexane (10:90) giving the triglyceride fraction plus some diol lipids. The 1st fraction was treated with
MeOH and HCl to give the corresponding esters, which were sepd. by preparative thin-layer chromatog. on silica using
hexane-Et2O (85:5). The band at Rf 0.60 was eluted with Et2O and the band 0.00 with MeOH; the latter band consisted
of diols which were then acetylated with Ac2O. Gas liq. chromatog. (GLC) of this mixt. disclosed the oil to contain
glycerol (1.4%) plus ethylene glycol, 1,3-propanediol, a significant amt. of 1,2-butanediol, and some 2,3-butanediol. GLC
of the band at 0.60 showed the %-acid compn. to be: lauric 0.33, myristic 0.11, palmitic 3.65, stearic 0.66, oleic 1.65,
linoleic 1.21.
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334. Thermal polymers of monoglycerides and their acetonized and acetylated derivatives
By Aldo Macchi, Roberto; Gallardo de Kuck, Isabel; Crespo, Fernando
From Grasas y Aceites (1968), 10(2), 32-6. Language: Spanish, Database: CAPLUS
The 1,2-isopropylidene glyceryl esters of tung oil fatty acids or α-ele ostearic acid were subjected to thermal polymn. at
250° in an inert atm. The main components of the polymers were dimers. A Diels-Alder addn. reaction with cyclization
(cyclohexene-ring formation) took place. Starting from these substances, the corresponding monoglycerides were
prepd.; the reaction was carried out at low temps. (50°) during 4 hr in an homogeneous phase without solvent and with
gradual addn. of H2O. On the other hand, the thermal polymers of the 1,2-isopropylidene glyceryl esters were acetylated
with a mixt. of HOAc and Ac2O using 85% H3PO4 as catalyst; in this way, the acetylated monoglycerides were obtained.
Because of the high proportion of OH groups, the monoglycerides could be emulsifiers and intermediate products; the
corresponding acetylated d erivs. could be used as plasticizers.
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335. Soil polysaccharides. II. Composition and properties of polysaccharides in soils under pasture and under
a fallow-wheat rotation
By Swincer, G. D.; Oades, John M.; Greenland, D. J.
From Australian Journal of Soil Research (1968), 6(2), 225-35. Language: English, Database: CAPLUS,
DOI:10.1071/SR9680225
Samples (0-6 cm.) of Urrbrae loam under pasture (P) for 16 years or under continuous alternate fallow-wheat rotation
(W) for 40 years were compared. P contained about 3-fold more carbohydrate than W. After removal of the light
fraction, extn. with N HCl and then with 0.5N NaOH followed by acidic acetylation removed 70-80% of the carbohydrate
from both soils; a single extn. with 0.2N NaOH removed 43-52% and 35-38% of the carbohydrate from W and P, resp.
The compn. of carbohydrate in given exts. and of neutral sugar in fractions from gel filtration of purified exts. was similar
for the 2 soils. Low-mol.-wt. fractions were rich in amino acids and glucose, ribose, and glycerol. Polymers of mol. wt.
4000-100,000 had relatively high amts. of uronic and amino acids, whereas those of mol. wt. >100,000 contained the
least amts. of amino acids but had appreciable quantities of deoxyhexoses indicative of microbial origin. Exts. with N HCl
removed more high-mol.-wt. material from P than from W. These exts. contained easily extractable recently synthesized
microbial polysaccharides. The soils had a higher proportion of low-mol.-wt. polymers during winter. Compared with P,
exts. of W had a greater proportion of uronic and amino acids and less ribose, arabinose, and deoxy sugars. Calcg. from
relative deoxy sugar contents, P contained 4-fold more microbial polysaccharide than W.
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336. Softening leather by application of an acetylated monoglyceride

By Curtis, Gerard W.
From U.S. (1968), US 3399954 A 19680903, Language: English, Database: CAPLUS
Aged leather is softened by swabbing it with liq. monoacetyl glycerol dioleate or liq. diacetyl glycerol monoleate which is
characterized by a sapon. no. of 375-85, an iodine no. of 50-60, and a monoglyceride content ≤1%. This treatment is
useful in the treatment of leather grips on golf clubs, uppers of shoes, and gloves.
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337. Polyformaldehyde with improved impact strength

By Kaufhold, Robert; Eifert, Werner
From Ger. (East) (1968), DD 61345 19680420, Language: German, Database: CAPLUS
The title material was prepd. by adding trimethylolpropane (I) plasticizer to stabilized polyformaldehyde (II). Thus, 100
parts of an acetic end-group stabilized II was treated with a soln. consisting of 1,1'-bis(2-hydroxy-3-tert-butyl-5-
methylphenyl)butane 0.3, a 38:35:27 caprolactam-hexamethylene adipate-hexamethylene sebacate polyamide 1, and I 4
in 86% aq. EtOH 200 parts. The compn. was homogenized 30 min., the solvent evapd., and the polymer dried at 80°/30
mm. The powd. polymer was extruded, the extrudate granulated, and the granulate injection molded into test samples
for the detn. of impact strength. Comparison of the above compn. with a similar one contg. glycerol (III) indicated that the
compn. contg. I had a higher impact strength without any redn. in tensile flexural strength than the compn. contg. III.
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338. Occurrence of an acylated inositol mannoside in the lipids of propionic acid bacteria
By Shaw, Norman; Dinglinger, F.
From Biochemical Journal (1968), 109(4), 700-1. Language: English, Database: CAPLUS, DOI:10.1042/bj1090700
Total lipid was extd. from Propionibacterium shermanii P23 cells with CHCl3-MeOH (2:1). A glycolipid fraction was
isolated from chromatog. on a silicic acid column eluted with Me2CO. Thin-layer chromatog. of this fraction with CHCl3-
MeOH-H2O (65:25:4) showed a single component with Rf 0.55. Alk. hydrolysis gave a nonreducing glycoside whose
paper chromatog. properties did not correspond to any known diglycosylglycerol. Total acid hydrolysis of the glycoside
showed the absence of glycerol and the presence of mannose and inositol. Acetylation of the glycoside with acetic
anhydride in pyridine gave a cryst. acetate, m.p. 173-4°, (α)D + 21°. The glycoside from P. shermanii may be identical to
O-α-D-mannopyranosyl-(1 → 2)-myoinositol, m.p. of the cryst. acetate 176-8°, [α]D + 25°, isolated as the degradation
product of phosphatidylmyoinositol mannoside from mycobacteria. Fatty acids of the glycolipid were probably esterified
to the inositol. A similar glycolipid was isolated from P. shermanii St 33, P. arabinosum, and P. freudenreichii. The latter
2 strains contained small amts. of glycolipids. Glycolipids in P. shermanii were ∼40% of the total lipid. The biosynthesis
of the glycolipid probably involved the transfer of mannose from GDP-mannose to an inositol acceptor. The acetylation
could occur before or after transfer of the sugar residue.
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339. New triterpenes of Alisma plantago-aquatica var orientale
By Murata, Tadakazu; Shinohara, M.; Hirata, T.; Kamiya, K.; Nishikawa, Masao; Miyamoto, M.
4039(01)98735-0
The lipid fraction isolated from the rhizomes of Alisma plantagoaquatica chromatographed repeatedly over silica gel
afforded 5 new triterpenes, amorphous alisol A (I, R1 = R2 = R3 = H) (II), C30H50O5, [α]D 99°; alisol B (III, R1 = R2 = H)
(IV), C30H48O4, m. 166-8°, [α]D 130°; alisol A monoacetate I (R1 = R3 = H, R2 = Ac) (V), C32H52O6, m. 194-6°, [α]D
86°; alisol B monoacetate III (R1 = H, R2 = Ac) (VI), C32H50O5, m. 162-3°, [α]D 121°; epialisol A (VII), C30H50O5, [α]D
81°. Mol. formulas were established by mass spectrometry and elemental analyses and sp. rotations taken at 21-8° in
CHCl3. Acetylation of II gave cryst. alisol A triacetate I (R1 = R2 = R3 = Ac) (VIII), C36H56O8, m. 231-3°, [α]D 56°,
N.M.R. δ 4.60 d, 4.8 m, v 3500 cm.-1 VIII reduced with NaBH4 and the product acetylated gave the pentol tetraacetate
(IX), C38H60O9, m. 193-4°. Both O.R.D. and circular dichroism curves of VIII showed strong pos. Cotton effects,
suggesting the presence of a 5α,3-ketone-like steroid moiety. II also gave pos. Liebermann-Burchard reaction and
Zimmermann test. II oxidized with HIO4 in dioxane yielded Me2CO and the tetranoraldehyde (X), C26H40O3, m. 190°,
[α]D 129°, v 3500, 2700, 1720, 1700 cm.-1, δ 9.58 t, 3.80 sextet. Treatment of II with Et2O-BF3 in Me2CO and
consequent acetylation gave the acetonide monoacetate (XI), C35H56O6, m. 213-15°, [α]D 75.5°, v 3480, 1745, 1705
cm.-1, δ 3.34 d, 3.59 m. The assumption was made that II was a tetracyclic terpene in which the isooctyl side chain
bears the glycerol moiety. II showed N.M.R. signals from 0.95-1.22 ppm. for 8 Me groups and X exhibited 6 Me groups.
The compds. showed relatively intense mass peaks at m/e 329 and 311, indicating loss of H2O. Deductions from
spectral observations did not lead to crucial evidence for the ring system and left the stereochemistry of the side chain
unclarified. II acetonide monobromoacetate (XII), C35H55BrO6, mol. wt. 651.71, crystd. from MeOH in orthorhombic
pillars, m. 185-6°. The 4 mol. unit cell had a 18.18, b 24.63, c 7.75 A., space group P212121, d. 1.247 g./cc.
Diffractometric measurement yielded 2237 diffractions about the c axis and coordinates of the Br atom were detd. by
calcn. of a 3-dimensional sharpened Patterson function. The structure was elucidated by successive applications of min.
function, least squares methods, and a Fourier synthesis; R value 0.142. The abs. configuration as shown was detd. by
using the anomalous dispersion of the Br atom. The structure of II was thus established with abs. configurations of the
side chain as 20R, 23S, 24R with A and B rings in boat conformation. V treated with K2CO3 in MeOH gave II; on
acetylation V was converted to VIII; and oxidn. of V with HIO4 yielded Me2CO and the amorphous trinoraldehyde (XIII), δ
9.40, 4.61, 3.80. Acetylation of IV gave III (R1 = R2 = Ac) (XIV), C34H52O6, m. 140-2°, [α]D 117.5°, δ 4.85, 4.49. IV
oxidized with HIO4 gave X, indicating the presence of a α-ketol in the side chain. VI on acetylation gave XIV and on
treatment with K2CO3 yielded IV. The N.M.R. spectrum of VI showed protons at C-11 and C-23 at δ 3.80, 4.49,
indicating that VI was alisol B 23-acetate. VII gave a triacetate, C36H56O8, m. 192-4°, [α]D 67.5°, mass spectrum
superimposable on that of VIII. Since VII on oxidn. with HIO4 gave Me2CO and X, it was concluded that VII is an epimer
of II at either C-23 or C-24.
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340. Monoglycerides and their acetylated derivatives, from maleic anhydride adducts of alpha-eleostearic acid
By Gallardo de Kuck, Isabel; Aldo Macchi, Roberto
From Grasas y Aceites (1968), 10(2), 37-40. Language: Spanish, Database: CAPLUS
Maleic anhydride adducts of tung oil total fatty acids and α-eleostearic acid were obtained by maleinization without
solvent. The corresponding tri-Bu esters were prepd. from the adducts by reaction with BuOH using concd. H2SO4 as
catalyst and PhMe as solvent. 1,2-Isopropylidene glyceryl esters were obtained from the tri-Bu esters by
interesterification with 1,2-isopropylidene glycerol using Na as catalyst; the anal. of the products showed an unchanged
Bu group. Combined acetone of the 1,2-isopropylidene glyceryl esters was split off to prep. the corresponding reddish-
brown, viscous liq. monoglycerides which had emulsifying properties; anal. showed that these substances were
dimonoglyceride mono-Bu esters (4-OH groups/mol.). Simultaneous decompn. and acetylation of 1,2-isopropylidene
glyceryl esters gave acetylated derivs. with properties similar to those prepd. by acetylation of dimonoglycerides with
Ac2O; the products were reddish-brown liqs. less viscous than the dimonoglycerides, with plasticizer properties; anal.
showed 4 Ac groups/mol.
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341. Homogeneous acetylation of dried cellulose fibers by using acetic anhydride gas
By Yoda, Tatsuro; Nomura, Ryo; Harada, Toshiyuki
From Jpn. Tokkyo Koho (1968), JP 43020255 B 19680830, Language: Japanese, Database: CAPLUS
Homogeneous acetylation of cellulose fibers with Ac2O in the presence of less than the amt. of a catalyst conventionally
used, such as NaOAc, was carried out by adding a polyhydric alc. into the catalyst soln. Thus, aq. solns. of NaOAc
contg. various amts. of polyethylene glycol having 1440 no.-av. mol. wt. were used as catalyst-soln. for the acetylation of
viscose rayon. The acetylation was carried out using Ac2O 47, HOAc 32, and air 21 mole % at 140° for 40 min. The
following results were obtained (% polyethylene glycol, % NaOAc, and % unacetylated product given): 0, 5, 100; 0, 20, 0;
5, 10, 50; 10, 10, 10; 30, 3, 50; 30, 5, 0; 30, 10, 0.
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342. Glyceride structure ofCardamine impatiens L. Seed oil

By Mikolajczak K L; Smith C R Jr; Wolff I A
From Lipids (1968), 3(3), 215-20, Language: English, Database: MEDLINE
A group of unusual triglycerides, in which one of the acyl groups is a vicinal dihydroxy acid with one of the hydroxyl
groups acetylated, has been isolated fromCardamine impatiens L. (Cruciferae) seed oil. Hydrolysis of these
triglycerides with castor bean lipase facilitated isolation and identification of a mixture of C(18), C(20), C(22), and C(24)
hydroxy acetoxy fatty acids. Pancreatic lipase hydrolysis data revealed that these monoacetylated dihydroxy acid
residues are esterified exclusively with one of the alpha-positions of the glycerol moiety. The remaining acyl groups
are comprised of ordinary C(18) unsaturated acids (which occupy 98% of the beta-position), palmitic acid, and C(20),
C(22), and C(24) monoenoic fatty acids.
~2 Citings
343. Glyceride structure of Cardamine impatiens seed oil

By Mikolajczak, Kenneth L.; Smith, Cecil Randolph, Jr.; Wolff, Ivan A.
A group of unusual triglycerides, in which one of the acyl groups is a vicinal dihydroxy acid with one of the hydroxyl
groups acetylated, has been isolated form C. impatiens seed oil. Hydrolysis of these trigylcerides with castor bean lipase
faciliatated isolation and identification of a mixt. of C18, C20, C22, and C24 hydroxy acetoxy fatty acids. Pancreatic
lipase hydrolysis data revealed that these monoacetylated dihydroxy acid residues are esterified exclusively with one of
the α-positions of the glycerol moiety. The remaining acyl groups are comprised of ordinary C18 unstad. acids (which
occupy 98% of the β-position), palmitic acid, and C20, C22, and C24 monoenoic fatty acids. 27 references.
~1 Citing
344. Extension of sugar chains through acetylenic intermediates. IV. Derivatives of 1-pentyne-D-erythro (and D-
threo)-3,4,5-triol
By Horton, Derek; Hughes, Jack B.; Thomson, J. Kenneth
From Journal of Organic Chemistry (1968), 32(2), 728-34. Language: English, Database: CAPLUS,
DOI:10.1021/jo01266a600
Ethynylation of 2,3-O-isopropylidene-aldehydo-D-glyceraldehyde (I) gives a 44:56 mixt. of 4,5-O-isopropylidene-1-
pentyne-D-erythro-(and D-threo)-3,4,5-triol (II and III), separable by gas liquid phase chromatog. as their resp. 3-acetates
(IV and V). Hemihydrogenation of IV and V gave the derived pentenes (VI and VII, resp.), also obtainable, in admixt., by
vinylation of I and acetylation of the product. The epimers were individually identified by degradation; IV and V were
ozonized and the products hydrolyzed to give an erythronolactone and a threonolactone, resp., and VI and VII
successively ozonized, reduced, and hydrolyzed to give erythritol and a threitol, resp. Sapon. of IV and V gave the sep.
resp. epimers II and III, which were converted into their resp. cryst. 3-(3,5-dinitrobenzoates) (VIII and IX). The esters (IV
and VIII) having the D-erythro configuration showed spin-spin couplings between H-3 and H-4 smaller than those of the
D-threo analogs (V and IX), indicating that the most populated rotamer state of these acetylenic derivs. is that having the
3-acyloxy group antiparallel, and the ethynyl group gauche to C-5. 27 references.
~0 Citings

345. Emulsifiers for whipped toppings
By Miles, John J., Jr.; Pader, Morton; Thompson, Stuart Wayne
From S. African (1968), ZA 6606377 19680421, Language: English, Database: CAPLUS
An emulsion is formed, essentially from a H2O-dispersible protein and glycerol diester in which 1 acid radical is derived
from AcOH and the other from a C12-24 fatty acid. Thus, a melted blend of coconut oil (hydrogenated to 1 I.V.) 33,
acetylated monoglycerides (from fully hydrogenated cottonseed oil with 1/2 of the free hydroxyls acetylated) 8, lard
monoglycerides 1.5, phosphoric acid esters of glycerides (partial Na salts of phosphoric acid esters of a mono-
diglyceride conc. made from 65 I.V. cottonseed oil) 0.2, lecithin 0.8, and color 0.0012 parts is added slowly with agitation
to an aq. soln. contg. Na caseinate 7, sucrose 49, and flavor 0.037 parts to form a rough emulsion. This emulsion is
homogenized and then spray-dried. Reconstituted mixts. of 59 g. dry powder in 1/2 cup cold milk are whipped 2, 3, and
4 min. to give non-bitter, bland-flavored, whipped creamlike products with overruns of 280, 300, and 310%. Dry powder
stored 4 months at 90°F. reconstitutes and whips with only slight decrease in % overrun which is superior to toppings
similarly prepd. with a propylene glycol monostearate-contg. mix or a lactylated glycerol monopalmitate-contg. mix. The
mixt. is used to prep. confectionery toppings similar to whipped cream.
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346. Determination of the distribution of the aliphatic groups of glyceryl ethers by gas-liquid chromatography of
the diacetyl derivatives
By Albro, P. W.; Dittmer, John C.
From Journal of Chromatography (1968), 38(2), 230-9. Language: English, Database: CAPLUS, DOI:10.1016/0021-
9673(68)85033-2
Alk-1-enyl glyceryl ethers (I) and alkyl glyceryl ethers (II) were obtained by hydrogenolysis of the parent lipids with LiAlH4
in Et2O, refluxing 30 min. The hydrogenolysis products were sepd. into 3 major fractions by silicic acid column
chromatog. Sterols and fatty acids were eluted with 40 ml. of 20% Et2O in hexane. I were eluted with 15 ml. of 45%
Et2O in hexane, and the II-contg. fraction with 20 ml. of H2O-satd. Et2O. Isolated I and II were acetylated and the
diacetates were gas-chromatographed on a 3% SE-30-Chromosorb W (acid-washed and hexamethyldisilazane-treated)
column at 230°. Acetates of fatty alcs. can be chromatographed on a 10% ethylene glycol adipate-Chromosorb W (acid-
washed) column at 185°. Ar carrier gas and an Ar ionization detector were used. Free and acetylated I were
characterized by Silica Gel G thin-layer chromatog. in 4 developing solvent systems, by chem. anal., and by ir
spectroscopy. The usefulness of the method for detg. the aliphatic group distribution in I of rat brain and in I and II of ox
brain ethanolamine phosphoglycerides is demonstrated. Of the total aldehyde, 94-96% was recovered after
hydrogenolysis and, of that, 90-95% was recovered in the I fraction isolated by column chromatog. The relative standard
deviation is generally ±5%.
~1 Citing
347. Combined substances of fatty oil from Helleborus abchasicus

By Dalakishvili, Ts. M.; Kemertelidze, E. P.
From Soobshcheniya Akademii Nauk Gruzinskoi SSR (1968), 51(3), 613-18. Language: Russian, Database: CAPLUS
A fatty oil was isolated in amts. of 15-18% from the subterranean parts of the title plant, after sepn. of the physiol. active
glycosides. This oil was subjected to an initial sepn. on a silica gel column. Investigation of the triglyceride fraction
followed, with 28 mg. being subjected to acidic methanolysis. Thin-layer chromatog. disclosed 3 materials. The zone
corresponding to the Me esters of the fatty acids was eluted with ether and the zone corresponding to the alcs. with
MeOH. The alcs., 6 mg. of polyols, were isolated and acetylated. Gas-liq. chromatog. (GLC) disclosed the 2 main
components to be glycerol and 1,2-butanediol. Similarly, the fatty acid Me esters were analyzed by GLC to det. the satd.
acids. The 3rd band, consisting of phospholipids, was isolated and found to comprise 0.38% of the fatty oil. The total
sterol content was 2.9%.
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348. Coating fruits

By Moore, Carl O.; Robinson, John W.
The fruit is contacted (dipping or spraying) with an aq. dispersion of amylose and an amylose plasticizer to form a
coating, and the coating is gelled on the surface of the fruit. Fruits which may be coated are dates, figs, dried fruits such
as prunes, apricots, and raisins, and candied fruits such as cherries, citron, citrus peel, etc. The amylose content in the
aq. dispersion may be 3-30% by wt. The amylose plasticizer may be glycerol, lecithin, choline chloride, corn sirup,
sorbitol, mannitol, dextrose, 1,2,6-hexanetriol, and acetylated glycerides. The wt. ratio of amylose plasticizer to amylose
may be 5:95 to 80:20. Thus, an aq. soln. of corn amylose was prepd. by heating a mixt. of 40 g. corn amylose and 360
g. water to 295°F. The sample was kept at 295°F. for 30 sec. The soln. was combined with an aq. dispersion prepd. by
mixing 40 g. "Myvacet" (distd., acetylated monoglyceride) and 2 g. polyoxyethylene sorbitan monostearate with 158 g.
hot tap water. Five lb. of raisins was placed on a screen and the aq. dispersion was sprayed on. The raisins were then
dried for 30 min. in an oven at 125°F. The raisins were thus coated with a transparent, glossy, noncoherent, gelled
coating. They were stored in closed jars for 1 week. At the end of the storage period the raisins poured freely and did
not clump or stick together.
~5 Citings
349. Antibacterial detergent compositions containing heavy metal salts of 2-pyridinethione-1-oxide

Detergent compns., having antibacterial qualities and useful as shampoos, comprise an org. surfactant 2-95, certain
H2O-sol. cationic polymers 0.1-4, and Zn, Cd, Zr, or Sn salts of 2-pyridinethiol-1-oxide 0.1-10% by wt. Preferred
surfactants are non-soap anionic and amorphous, zwitterionic or polar non-ionic or mixts. thereof, such as Na coconut-
alkyl glycerol ether sulfonate (I), Na tallow-alkyl glycerol ether sulfonate (II), triethanolamine coconut-alkyl sulfate,
monoethanolamide of coconut fatty acids, etc. Desirable polymers, having mol. wts. of 3000-100,000, are reaction
products of polyethylenimine (III) with ethylene oxide or propylene oxide in ≥ 1:1 ratio. Thus, a mixt. of I (∼23% di- and
the balance mono-glycerol) 25.0, II (∼23% di- and balance mono-glycerol; satd. tallow alcs. ∼C14 2, C16 32, and C18
66%) 3.0, NaCl 6.7, Na2SO4 3.3, Na N-lauroylsarcosinate 3.8, N-(coconut-acyl)sarcosine 1.2, coconut fatty acid
diethanolamides 2.0, acetylated lanolin 1.0, perfume 0.4, color 0.04, Zn 2-pyridinethiol-1-oxide (av. particle size 2 µ) 2.0,
III (mol. wt. 40,000-60,000)-ethylene oxide reaction product (wt. ratio 1:1, mol. wt. 80,000-120,000) 0.5%, and the
balance H2O, gave a stable cream. This compn. had excellent cosmetic and antidandruff properties, and both the
degree of deposition of the Zn salt and the residual antibacterial activity of surfaces washed with the compn. were greater
than those of similar products contg. no polymer.
~5 Citings
350. Water-soluble films from partially acetylated high-amylose corn starch

By Mark, Arthur M.; Mehltretter, Charles L.
From Staerke (1969), 21(4), 92-6. Language: English, Database: CAPLUS, DOI:10.1002/star.19690210403
A 70% high-amylose cornstarch of 12-25% H2O content was esterified by Ac2O to a substitution degree of 0.10-0.31.
No disintegration of granules and no degradation occurred during acetylation. Esters with a degree of substitution (d.s.)
of 0.21-0.50 were sol. in hot H2O (1% concn.). Films cast from esters of d.s. 0.21 and 0.31 had tensile strengths of 6000
psi. and no O permeability, but lacked clarity and flexibility due to a high percentage of insolubles contg. swollen
granules. Granule disintegration took place after neutralization of the free HOAc by steam-jet cooking, autoclaving,
ultrasonic irradn., and Me2SO treatment. Jet cooking combined with clarification gave a completely sol. product with
very high clarity and max. flexibility and strength. Intrinsic viscosity measurements showed that only the ultrasonic
treatment degraded the ester. Amylograph viscosity behavior showed that jet cooking resulted in extensive granule
disintegration. Retention of high flexibility at 20-30% relative humidity requires plasticization with 25% glycerol. Films of
d.s. 0.21-0.31 were nearly completely sol. in boiling H2O and remained sol. on cooling. Jet-cooked and clarified esters of
d.s. 0.25-0.31 are expected to yield films completely sol. in hot and cold H2O having good potential as edible packaging.
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351. Synthesis of galactosyl glycerides and related lipids

By Wehrli, H. P.; Pomeranz, Y.
From Chemistry and Physics of Lipids (1969), 3(4), 357-70. Language: English, Database: CAPLUS,
DOI:10.1016/0009-3084(69)90041-3
The synthesis of natural mono-D-galactosyl glycerides is reported. The synthesis involves acylation of the primary
hydroxyl groups of 2,5-O-methylene-D-mannitol, cleavage of the mannitol moiety between C-3 and C-4 by Pb(OAc)4,
redn. of the resulting aldehyde, attachment of D-galactose by the Koenigs-Knorr reaction, hydrolysis of the acetal,
acylation of the hydroxyl group, and hydrazinolysis of the acetylated glycolipids. A simplified procedure, in which the
optical activity at C-2 of the glycerol moiety is lost, is also described.
~21 Citings
352. Soap containing Polycomplex A, useful for removing oily stains

By Martineau, Jean; Biechler, Francois J.
Soaps or detergents contg. 2-40% Polycomplex A (exact chem. formula unknown) as the active ingredient are prepd.
These compns. are esp. useful for removing oily stains from clothing and human skin. Thus, a liq. soap was prepd. from
Na laurylsulfonate 20, glycerol 1.5, acetylated lanolin 2.5, water 50, Polycomplex A 25, and perfume 1 kg.
~0 Citings
353. Qualitative and quantitative determination of alcohols added to a composition of mixed polyesters of
terephthalic acid
By Kochnova, Z. A.; Sorokin, M. F.; Grafkin, B. N.; Shabanova, N. P.
Paper chromatog. was used for the qual. detn. and gas chromatog. for the quant. detn. of ethylene glycol (I), 1,3-
propylene glycol (II), 1,4-butylene glycol (III), diethylene glycol (IV), glycerol (V), and trimethylolpropane (VI) or their
binary mixts. Paper chromatog. was carried out according to P. Fijolka's (1963) procedure. The following Rf values were
found when 10:10:1 C6H6-acetone-water solvent system was used (compd. and Rf given): I, 0.225; II, 0.350; III 0.390;
IV, 0.300; V, 0.050; VI, 0.775. Gas chromatog. was performed using a 2-m column filled with 75 Chromosorb W
impregnated with 25 parts acetylated dextrin (O. French, 1957). The following elution times (t) were obtained when the
column temp. was 225° and He (carrier gas) velocity was 90 ml/min (compd. and t in min given): I, 0.83; II, 1.00; III, 2.66;
IV, 2.67; V, 4.84; VI, 8.00; triethylene glycol, 7.35. To obtain the quant. results, the sensitivity coeffs. (K) were detd. for
each glycol; K = peak area/compd. wt. K were not dependent on compd. concn. in the sample (compd., % concn. in
EtOH, and K given): I, 10, 2240; I, 20, 2254; V, 20, 653; VI, 20, 2500. To analyze a sample of polyester it was 1st
sapond. with KOH soln. The pptd. K salts were filtered off, the excess KOH was pptd. with CO2, and the remaining
filtrate evapd. to leave glycol mixt. which was then analyzed as above.
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354. Polyolefin-modified polyurethanes for coatings and adhesives

By Kales, Rene
Polyolefin-modified polyurethanes were prepd. by dissolving a polyolefin in a fatty acid ester having ≥1 free OH group
and treating a polyisocyanate with the resulting soln. The modified polyurethane products were used as surface coatings
and adhesives. Thus, a mixt. of hard boiled linseed oil 68.0, polyethylene of mol. wt. 12,000 112.0, ethylene glycol (I) 30,
and Ca naphthenate 0.5 was heated at 250°, under N, for 2 hrs. The soln. was cooled to 50° and 41.0 g. 80:20 2,4-
tolylene diisocyanate and 2,6-tolylene diisocyanate mixt. was added along with 221.5 g. xylene. The temp. of the mixt.
was kept at 60-5° until the desired viscosity had been attained. The temp. was then reduced to 35-40° and MeOH 9.0,
Co naphthenate 0.1, lead naphthenate 1.2, and antiskinning agent 0.5 g. were added. The mixt. was filled and kept in
closed containers until used. The compn. was suitable for prepg. coatings which had excellent hardness, elasticity, and
abrasive resistance. In place of the hard boiled linseed oil, soybean oil, tall oil, or castor oil could be used, while glycerol,
Polyether 15-100, and other polyhydric alcs. such as sorbitol could be used in place of I. Also the polyethylene could be
directly dissolved in fatty acid compds. contg. free OH groups such as alkyl ricinoleates and acetylated alkyl ricinoleates.
The compns. were admixed with sand and (or) cement and used to repair concrete and cement structures and asphalt
shingles. The coating mixts. can be converted into rubber-like synthetic elastomers which had excellent elongation, high
tensile and tear strength, and high resistance to abrasion and oxidn. The rubbers can be readily cast into molds and
were of particular value as shock absorbent pads under machinery where vibration or impact shock is a problem.
~1 Citing
355. New sources of 9-D-hydroxy-cis-12-octadecenoic acid

By Powell, R. G.; Kleiman, R.; Smith, Cecil Randolph, Jr.
9-D-Hydroxy-cis-12-octadecenoic acid has been isolated from 3 seed oils o f the family Apocynaceae: Holarrhena
antidysenterica (73%), Nerium ole ander (11%) and N. indicum (8%). The known occurrence of this acid was previously
limited to the genus Strophanthus (9-15%). A mixt. of unusual tetra-acid glycerides was isolated from N. oleander oil by
thin layer chromatog. Pancreatic lipase hydrolysis of the glyceride mixt. showed that 9-D-acetoxy-cis-12-octadecenoic
acid is esterified exclusively at an α-glycerol position and that normal fatty acids occupy the remaining 2 glycerol
positions. A portion of the hydroxy acid in N. indicum oil was also acetylated, however, no acetate was found in either H.
antidysenterica or S. hispidus oils.
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356. Monacetin. Pharmacochemistry and pharmacology of a specific antidote against poisoning with
fluorocarbon compounds
By Bernasconi, Raymond
From Pharmaceutica Acta Helvetiae (1969), 44(3), 149-69. Language: German, Database: CAPLUS
Com. monacetin samples were examd. for impurities by thin-layer chromatog. on silica gel G with 60:40 Me2CO-CHCl3
and by gas chromatog. on Apiezon-M. Diacetin, triacetin, glycerol, polyglycerols, 3-chloro-1,2-propanediol,
isopropylideneglycerol, and acetylisopropyli-deneglycerol were the major impurities. Monacetin was synthesized by (a)
esterification of glycerol with HOAc, (b) esterification of glycerol with Ac2O-pyridine, (c) glycerinolysis of triacetin, (d)
acetylation of HOCH2CH(OH)CH2Cl, and (e) acetylation of isopropylideneglycerol, followed by sapon. Glycerol 1-
acetate was obtained in 44-72% yield and methods (b) and (c) were most satisfactory. The impurities were glycerol 1,3-
diacetate, glycerol triacetate, H2O, and HOAc. The viscosity of monacetin was 155 cp. at 20° and 48 cp. at 37°. It was
hygroscopic, but could be sterilized by dry heat at 160° 90 min. The sapon. of all 3 acetins was a first order reaction.
The lowest sapon. rate was observed at pH 4.2 ± 0.2. Aq. monacetin was storage stable for ∼8 months at 20°. Pharm.
compns. of monacetin are recommended.
~1 Citing
357. Liquid tooth paste suspensions

By Salzmann, Gerhard M.
A stable tooth paste suspension with improved cleaning properties is prepd . from glycerol 20, polysaccharide 0.8,
BZONa 0.5, saccharin Na salt 0.5, H2O 61.7, Na lauryl sulfate 3, Na metaphosphate (I) 10, anhyd. Ca3(PO4)2 (II) 1, and
aroma 2.5%. The polysaccharide is a high mol. wt. product contg. mannose, glucose, K glucuronate, and acetylated
residues (2:1:1:1). Hydrated Al2O3 may be used instead of I and II. The suspension may contain stannous fluoride or
Na monofluorophosphate.
~0 Citings
358. Isomers of glucosaminylphosphatidylglycerol in Bacillus megaterium

By MacDougall, J. C.; Phizackerley, P. J. R.
From Biochemical Journal (1969), 114(2), 361-7. Language: English, Database: CAPLUS, DOI:10.1042/bj1140361
The lipids of B. megaterium were extd. and 3 lipids contg. glucosamine were identified. One of these is not a
phospholipid, but the other 2, which differ in their chromatographic behavior, contain P, glycerol, fatty acid, and D-
glucosamine in the molar proportions 1:2:2:1. In both phosphoglycolipids, the fatty acids are bound in ester linkage, and
both yield 2,5-anhydromannose and 3-sn-phosphatidyl-1'-sn-glycerol on treatment with NaNO2. Both phosphoglycolipids
were N-acetylated and, after removal of fatty acids by mild alk. hydrolysis, in both cases N-acetylglucosamine was quant.
released by β-N-acetylhexosaminidase. The glucosaminylglycerols derived from the 2-phosphoglycolipids by partial
acid hydrolysis differ in their behavior towards periodate. In one case 1 mole of periodate is rapidly consumed per mole
of glucosaminylglyc-erol, but in the other case under identical conditions the consumption of periodate is negligible. The
phosphoglycolipids were identified as 1'-(1,2-diacyl-sn-glycero-3-phosphoryl)-3'-O-β-(2-amino-2-deoxy-D-
glucopyranosyl)-sn-glycerol and as 1'-(1,2-diacyl-sn-glycero-3-phosphoryl)-2'-O - β - (2 - amino - 2 - deoxy - D-
glucopyranosyl)-sn-glycerol. Both phosphoglycolipids are good substrates for phospholipase A: neither is a substrate for
phospholipase C from Clostridium perfringens, and only the 3'-glucosaminide is a substrate for phospholipase D.
~2 Citings
359. Isomers of glucosaminylphospatiylglycerol in Bacillus megaterium

By MacDougall J C; Phizackerley P J
From The Biochemical journal (1969), 114(2), 361-7, Language: English, Database: MEDLINE
1. The lipids of Bacillus megaterium were extracted and three lipids containing glucosamine were identified. One of
these is not a phospholipid, but the other two, which differ in their chromatographic behaviour, contain phosphorus,
glycerol, fatty acid and d-glucosamine in the molar proportions 1:2:2:1. 2. In both phosphoglycolipids, the fatty acids
are bound in ester linkage, and both yield 2,5-anhydromannose and 3-sn-phosphatidyl-1'-sn-glycerol on treatment with
sodium nitrite. 3. Both phosphoglycolipids were N-acetylated and, after removal of fatty acids by mild alkaline
hydrolysis, in both cases N-acetylglucosamine was quantitatively released by beta-N-acetylhexosaminidase. 4. The
glucosaminylglycerols derived from the two phosphoglycolipids by partial acid hydrolysis differ in their behaviour
towards periodate. In one case 1 mole of periodate is rapidly consumed/mole of glucosaminylglycerol, but in the other
case under identical conditions the consumption of periodate is negligible. 5. The phosphoglycolipids were identified
as 1'-(1,2-diacyl-sn-glycero-3-phosphoryl)-3'-O-beta-(2-amino-2-deoxy-d-glucopyranosyl)-sn-glycerol and as 1'-(1,2-
diacyl-sn-glycero-3-phosphoryl)-2'-O-beta-(2-amino-2-deoxy-d-glucopyranosyl)-sn-glycerol. 6. Both
phosphoglycolipids are good substrates for phospholipase A: neither is a substrate for phospholipase C from
Clostridium perfringens, and only the 3'-glucosaminide is a substrate for phospholipase D.
~3 Citings
360. In vivo "quantum" synthesis of reserve waxes in seeds of Murraya koenigii

By Kartha, A. R. S.; Singh, Satzendra Pal
From Chemistry & Industry (London, United Kingdom) (1969), (38), 1342-3. Language: English, Database: CAPLUS
The lipids in seeds of M. koenigii are a mixt. of reserve waxes and hydrocarbons. The mature seed kernels of M. koenigii
gave 3.5% waxy lipids when extd. with CCl4. After purification, the lipids gave an I value A (Hanus technique) of 208-210
and I value B (technique of A. R. S. Kartha and H. S. Nainawati, 1963) of 353-354. The lipids showed a Hehner value of
96-97 and mixed acids were sepd. into acidic and neutral fractions by washing in hexane with 10% aq. alc. contg. 1%
KOH. The acids amounted to 17% on a refined lipid basis and showed an approx. mean mol. wt. of 384 corresponding
to a mixt. of C24 and C26 acids and I values A and B of 112 and 153, resp. The neutral fraction amounted to 69% and
showed I values A and B of 151 and 300, resp. Both acidic and neutral fractions contained considerable polyethenoid
and conjugated unsatn. During processing some material sepd. as a hexane and alkali-insol. dark mass and gave the
same value of 133 for the I values A and B. The hexane sol. neutral material showed a hydroxyl value of 35 by the
gravimetric acetylation procedure. The glycerol produced during hydrolysis was estd. by a std. acetylation procedure and
amounted to 0.1% on a lipid basis. A study of the biosynthesis of the waxes showed that the lipid content of the kernels
at seed development stages of 17, 25, 34, 44, 57, 69, and 100 were 4.7, 4.4, 4.1, 3.8, 3.5, 3.4, and 3.4%, resp.,
corresponding to lipid development stages of 23, 32, 41, 50, 59, 69, and 100, resp. The seeds showed a decrease in
percentage lipid content with maturity, but the total lipids per seed progressively increased.
~2 Citings
361. Edible collagen sausage wrap

By Cohly, Mauj A.
From Ger. Offen. (1969), DE 1809767 19690604, Language: German, Database: CAPLUS
Fresh, frozen, or corned meat skin, which has been cleaned of fat and muscle, hair, and epidermis, is ground at around
20° into a paste of finely divided collagen, and suspended in water. The paste swells in an acid soln. (pH 2.5-3.7) and is
manipulated and extruded in a tube form which later is coagulated in a soln. of an org. Al complex salt with an Al content
of 1.5-5.0% in the finished product. The tube is passed through a second tanning soln. contg. 0.01-5.0% glutaraldehyde,
and the tanned tube is washed, softened, and wound. The org. complex salt is prepd. from a soln. of 10-20% Al2(SO4)3,
admixed with 3-7% Na citrate to obtain a complex, together with 3-7% Na2CO3. The softening bath was aq. glycerol
with an acetylated fatty acid glyceride added as an emulsifier if necessary.
~0 Citings
362. Edible collagen sausage casings

By Cohly, Mauj A.; Sanner, James W.
From Ger. Offen. (1969), DE 1802683 B2 19730816, Language: German, Database: CAPLUS
Subsequent to removal of epidermis and hair, the corium layer of fresh, frozen, or salt-treated (limed or unlimed) animal
hides is ground in water (<20°) to a collagen suspension, treated with an acid at pH 2.5-3.7, and compressed through a
circular extruder to form a tubular casing. The extruded casing is immersed in a coagulation bath, tanned with a nontoxic
tanning agent (plant origin) or with an edible dialdehyde such as glutaraldehyde, washed, and processed in a plasticizer
and fattener bath contg. a plasticizer in an emulsion contg. 0.5-5.0% by wt. of a fatty acid monoglyceride and (or) an
acetylated fatty acid monoglyceride and ∼10% of this amt. of an emulsifier soap or a detergent [such as Na dodecyl
sulfate or sorbitan poly(oxyethylene)monoalkanoate]. The dried casing contains 0.05-0.5% by wt. of monoglyceride.
Thus, the corium of conventionally treated cattle hides was neutralized, delimed, cut to sq. pieces of 0.6-10-cm edge
length, ground to a particle size of ∼1 mm, treated with dil. lactic acid, and swollen overnight by allowing to stand at 3°.
The thin paste contg. ∼4% collagen and 1.2% lactic acid was homogenized and filtered, compressed to casings, and
coagulated in an aq. soln. of 40% (NH4)2SO4, and tanned in a soln. contg. ∼10% Al2(SO4)3· 18 H2O, 3-7% Na citrate,
and 3-7% Na2CO3, ∼pH 4.0. After washing, the casings were processed repeatedly for 3-10 min in a plasticizer bath
contg. 0.5-5.0% glycerol monostearate diacetate emulsified with 0.05-0.5% Na dodecyl sulfate, dried, and stored until
use.
~1 Citing
363. Acceleration of cellulose acetylation

By Kadyrova, S. A.; Aikhodzhaev, B. I.; Pogosov, Yu. L.
From Doklady Akademii Nauk UzSSR (1969), 26(10), 29-30. Language: Russian, Database: CAPLUS
The addn. of 2% ethylene glycol (I) to acetylating mixt. (AcOH, Ac2O, H2SO4) increases the cellulose acetylation rate 2-
3 times. I can also be used in the activation of cellulose together with AcOH (2-4% I, 18-20°, 18 hrs). Other hydroxy
compds. (MeOH, EtOH, iso-BuOH, allyl alc., glycerol, pentaerythritol, or mannitol) have lower activating ability than I.
~2 Citings
364. Zein-containing plastic composition

By Martin, Doris N.
Zein is mixed with a specific amt. of a plasticizer and optionally a white pigment to give a free-flowing powder blend that
forms a flexible, pliable, mass on the addn. of warm water. The compn. is used as a modeling clay. Thus, 37.5 g zein
was blended with 2.5 g glyceryl monoricinoleate and 2.5 g TiO2 and the compn. was placed in a polyethylene bag and
kneaded with 30 ml hot tap water for 2-3 min to give a plastic lump. The plastic was molded into jewelry forms, which
were allowed to dry overnight to give leathery, firm, noncracking pieces. The forms were immersed in a H2O-sol. dye for
5 hr to give uniform, bright, dyeing. Similar compds. were prepd. by using polyethylene glycol or an acetylated
monoglyceride.
~5 Citings
365. Use of acetylated derivatives of stearic acid monoglycerides in cosmetic creams

By Shmidt, A. A.; Van'yan, M. L.; Lekhter, A. E.; Shur, S. I.; Ob'yakova, G. S.; Antropova, S. K.; Kabanova, E. V.;
Kalinina, R. A.; Markina, V. V.
From Maslozhirovaya Promyshlennost (1970), 36(1), 32-4. Language: Russian, Database: CAPLUS
The influence of different factors on the degree of acetylation of stearic acid monoglycerides, m. 52.9° (44.8% of
monoesters, 5.4% of glycerol, acid no. 5.0 mg/-KOH, sapon. no. 160.8 mg KOH, iodine no. 18.5, and hydroxyl no. 285.2
mg KOH) with Ac2O was studied. Thus, 1 hr acetylation at 140° at the ratio Ac2O-hydroxyl equiv. 0.4 gave 65.3%
conversion and at the ratio 1.6, 99.2% conversion, resp. In the latter case, acetylmonoglycerides (I), m. 26.5°, with acid
no. 2.5 mg KOH, hydroxyl no. 2.5 mg KOH, and sapon. no. 320.9 mg KOH were obtained. The degree of conversion
was independent of the reaction temp. and time in the studied ranges (110-40° and 1 hr-4 hr, resp.). In lab. test
(described in detail), I did not exhibit emulsifying properties, but had considerable plastifying effect, which was tested on
two creams made in the USSR.
~0 Citings
366. Suntan formulations

An alkali-sol. copolymer contg. an ethylenically unsatd. deriv. ofphenyl salicylate, benzophenone, or benzotriazole and an
ethylenically unsatd. carboxylic acid is formulated at >1% in an oil-in-H2O emulsion, an org. solvent soln., or a solid gel,
to give a suntan compn. that absorbs uv radiation, causing sunburn while transmitting uv radiation causing tanning of the
skin. Thus, a 5:4:1 mixt. of 2-hydroxy-3-(2-hydroxybenzyloxy)propyl methacrylate, β-hydroxypropyl acrylate, and acrylic
acid was refluxed at 83° for 6 hr in the presence of a free-radical catalyst to give a terpolymer which was dissolved in iso-
PrOH to give a 50%-solids soln. The soln. 1.4 was dild. with EtOH 23.6 and iso-Pr myristate 3, phenylmethylpolysiloxane
1, and glycerol 1 part and a trace of perfume was added to give a suntan formulation that was not removed by freshor
salt water, but was readily removed by soap and water. Other copolymers used contained 2-hydroxy-3-(2-
hydroxyphenoxy)propylacrylate, β-hydroxyethyl acrylate, methacrylic acid, Et acrylate, Ph 2-hydroxy-5-
(methacryloxymethyl)benzoate, Bu acrylate, Ph 2-hydroxy-5-(acryloxymethyl)benzoate, itaconic acid, the 4-(3-
methacryloxy-2-hydroxypropyl) ether of 2,4-dihydroxybenzo-phenone, vinyl acetate, Et H maleate, the 4-(3-acryloxy-2-
hydroxypropyl) ether of 2-(2,4-dihydroxyphenyl)benzotriazole, Bu H fumarate, and the 3-(3-methacryloxy-2-
hydroxypropyl) ether of 2-(2,3-dihydroxyphenyl)benzotriazole. Other suntan formulations contained acetylated lanolin,
stearic acid, beeswax, mineral oil, a water- and alc.-sol. lanolin deriv., butylated hydroxyanisole, and NH4OH.
~0 Citings
367. Structure of mycolic acids and of an intermediate in the biosynthesis of dicarboxylic mycolic acids
By Laneelle, Marie Antionette; Laneelle, Gilbert
From European Journal of Biochemistry (1970), 12(2), 296-300. Language: French, Database: CAPLUS
The lipids of mycobacteria contain mycolic acids, which are C70-80 α-alkyl-β-hydroxy acids. Mycolic acids isolated from
a strain of Mycobacterium paratuberculosis RCH(OH)(C22H45)CO2H with R contg. 2 cyclopropanes (I); with an oxo
group (II); and with a carboxyl group (III) were studied. The elucidation of the structure of the dicyclopropanic mycolic
acid (I) was carried out by mass spectrometry of the acetylated ester, after chromic oxidn., and R was Ia. In the keto
mycolic acid (II), R was Me-(CH2)17CHMeCO(CnH2n-2)(n = 34-9). In the dicarboxylic mycolic acid (III), R was
HO2C(CnH2n-2) (n = 32-9). Etemadi suggested that the dicarboxylic acids are produced from the keto mycolic acids by
a biol. Baeyer-Villiger oxidn. and postulated an ester of the dicarboxylic acid (III) as an intermediate. This compd. was
isolated, and its structure established by alk. hydrolysis, pyrolytic gas chromatog., and mass spectrometry as Me-
(CH2)17CHMeO2C(CnH2n-2)CH(OH)CH(C22H45)CO2H (n = 32-9). This compd., "mycolic wax," has either a free
carboxyl, or is linked to glycerol to form a 1-monoglyceride; the glyceride is identified by mild hydrolysis and periodate
oxidn. on thin layer chromatog. Some further comments on the biogenesis of mycolic acids are added.
~11 Citings
368. Preparation of collagenic products, especially edible sausage casings with great resistance to moisture and
dryness
By Cohly, Mauj A.; Sanner, James W.
From Ger. Offen. (1970), DE 1941039 A 19700219, Language: German, Database: CAPLUS
Collageneous sausage casings are prepd. from limed or unlimed hides by a new coagulation and neutralization
treatment. By addn. of suitable plasticizers, improved properties are obtained with respect to filling and cooking. Fresh,
frozen, or salted limed or unlimed hides are swollen, depilated mech., and split to obtain a corium layer, which is finely
ground and treated to obtain a paste. A weak acid is added to obtain an extrudable paste contg. 2-6% dry matter. The
paste is pressed through a circular nozzle in a coagulation bath contg. (NH4)2SO4, Na2SO4, or a similar compd. and a
sufficient amt. of a strong alkali, such as NaOH, to completely neutralize the acid. The neutralization may take place
partially in the coagulation bath and be completed in a neutralization bath. By neutralization, the coagulated collagen is
hardened and tanning of the extruded collagen is made unnecessary. The neutralized casings are washed and treated
in an aq. soln. of glycerol or an equiv. plasticizer, preferably contg. an acetylated or nonacetylated fatty acid
monoglyceride. The casings are dried and rolled up. Thus, selected hides (30-4 kg) were washed and freed of muscle
residues, etc., immediately after stripping. The hides were treated for <6 hr with an aq. soln. contg. 6 wt. % fresh ca
(OH)2, 1.5 wt. % NaHS, and possibly ≤3% dimethylamine sulfate in ∼450 wt. % H2O (15-20°). The hides are removed
and hung up for ∼30 min, after which they are split into 2 equal parts by wt. The outer hide is removed and the inner wall
introduced into a vessel contg. 4.5 times the wt. of the hides of H2O (15°) and washed for 20-30 min; the wash water is
removed and H2O added again. Lactic acid (58-115 g 44% lactic acid/l. cold H2O) is added in small portions at 15-min
intervals; the bath temp. must be maintained at <32°. The endpoint is reached at a pH <7.0. The hides are washed with
15° H2O, packed in polyethylene bags, and cooled. The hides are cut into small pieces and ice is added during grinding,
to maintain the temp. <20°, preferably <10°, in several phases to <1.2 mm. The mash is dild. with H2O (90% H2O and
10% collagen), the pH brought to 2.5-3.7 with dil. lactic acid (also with citric acid or HOAc) and kept overnight at 3°. The
collagen is maintained with H2O and acid at pH 2.5-3.7. The mass contg. 4% collagen and 1.2% lactic acid is
homogenized, filtered, and deaerated. The entire treatment, after washing the limed hides, takes 6-12 hr. The mash is
extruded under pressure into a coagulation bath contg. 40% (NH4)2SO4 or Na2SO4. The collagen fibrils are
dehydrated, dild. again, and brought into a 2nd coagulation bath contg. 5% (NH4)2SO4, 10% NaCl, and 0.5% NaOH,
and subsequently introduced into a series of washing troughs and treated with a soln. contg. 5% glycerol and 1%
acetylated fatty acid monoglycerides. The casings are dried, blown up, dried with air, and partially remoistened.
~1 Citing
369. Identification of polyglycerols by thin-layer chromatography of their acetates

By Dallas, Michael S. J.
9673(01)85550-3
The method of S. Dittrich (1966) for detg. the no. of OH groups in polyalcs., by a partial acetylation of the sample and
subsequent thin-layer chromatog. of the products, was adapted for the identification of polyglycerols. For an in situ
acetylation on the thin-layer plates, 1:1 silica gel G-Kieselguhr G mixed plates contg. CaCl2 were used, and the
polyglycerols were developed with 55:30.5:14.5 EtOAc-iso-PrOH-H2O, acetylated by spraying with 60 vol. % Ac2O in
pyridine and heating 15 min at 95-100°, and developed in the 2nd dimension with 10:102:6:2 cyclohexane-Et2O-EtOH-
HCO2H. The spots were visualized by using the thymol reagent of S.Adachi (1965). A characteristic pattern of spots
was obtained with com. polyglycerols, which can be used for a qual. comparison of different samples.
~0 Citings
370. Extraction and partial purification of two histone-specific transacetylases from rat liver nuclei
By Gallwitz, Dieter
CAPLUS, DOI:10.1016/0006-291X(70)91072-7
Two histone-specific transacetylases with an approx. mol. wt. between 80,000 and 90,000 were solubilized from rat liver
nuclei by sonication in the presence of 1M (NH4)2SO4 and 20% glycerol followed by pptn. with 3.5M (NH4)2SO4. A 50-
fold purification was achieved by DEAE-cellulose and Sephadex G-200 chromatog. The acetate transferred by the
enzymes from acetyl coenzyme A to histones is N-linked. The pH-optimum of the enzymic acetylation is ∼8.6.
~0 Citings
371. Cyclic glycerol acetals. III. Acetoxy-, chloro-, and benzoxyloxy acetals
By Gelas, Jacques
From Bulletin de la Societe Chimique de France (1970), (6), 2349-54. Language: French, Database: CAPLUS
The acetylation, chlorination, and benzoylation reactions of I (R = OH) and II (R = OH) were examd. I (R = OH) were
treated with AcCl in pyridine to give the cis and trans isomers of I (R = OAc) while II (R = OH) similarly gave II (R = OAc).
Similar treatment with SOCl2 gave III. I (R = Cl) and II (R = Cl), were obtained by acetylating glycerol monochlorohydrin.
Benzoylation with BzCl in pyridine gave I (R = OBz) and II (R = OBz).
~0 Citings
372. Acetylated glycol ricinoleate as primary plasticizers for polyvinyl resins

By Jain, Ajai K.; Bhatnagar, Rajendra K.
From Journal of the Oil Technologists' Association of India (Mumbai, India) (1970), 2(1), 12-15. Language: English,
Database: CAPLUS
Compds. prepd. by interesterification of castor oil and different glycols followed by acetylation or by acetylation and
epoxidn. were blended with poly(vinyl chloride) resin, and the tensile strength, elongation, volatility, thermal stability, and
solvent and H2O extn. losses were measured. Epoxidized acetylated glycol esters prepd. from ethylene glycol, 1,3-
butanediol, or diethylene glycol showed good compatibility with the resins and were suitable for primary plasticization,
being almost equal to dioctyl phthalate (I). These compds. gave products with lower volatility losses than I.
~1 Citing
373. Synthesis of galactosyldiglyceride

By Bashkatova, A. I.; Smirnova, G. V.; Volynskaya, V. N.; Shvets, V. I.; Evstigneeva, R. P.
From Doklady Akademii Nauk SSSR (1971), 201(5), 1231-3 [Biochem]. Language: Russian, Database: CAPLUS
The ortho ester method was used to synthesize 1,2-di-O-palmitoyl-3-O-β-D-galactopyranosyl-sn-glycerol (I) by 2
alternative routes. In the 1st route, the 1,2-diglyceride was treated with an equimolar amt. of monosaccharide
orthoacetate using lutidine perchlorate as the catalyst in boiling PhCl to yield I tetraacetate after azeotropic removal of
H2O; in the 2nd route, this reaction was run by transesterification in the presence of p-MeC6H4SO3H in refluxing
C2H4Cl2 to give 3,4,6-tri-O-acetyl-1,2-O-(1,2-di-O-palmitoyl-sn-glyceryl-3-O-orthoacetyl)-β-D-galactopyranose (II). II
was isomerized to the acetylated 1,2-trans-glycoside by heating with 2,2'-bipyridyl perchlorate in C2H4Cl2. 1,2-O-
Isopropylidene-sn-glycerol and an equiv. amt. of galactose orthoacetate gave 10% 1,2-O-isopropylidene-3-O-(2,3,4,6-
tetra-O-acetyl-β-D-galactopyranosyl)-sn-glycerol. 1,2-O-Isopropylidene-sn-glycerol was converted to 50% 3,4,6-tri-O-
acetyl-1,2-O-(1,2-O-isopropylidene-sn-glyceryl-3-O-orthoacetyl)-α-D-galactopyranose, which was isomerized as above to
give 45% tetraacetate (III). The Me2CH protective group in III was removed by treatment with 50% AcOH at room temp.
to form 1-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-sn-glycerol, which reacted with palmitoyl chloride in pyridine to
give the dipalmitoyl deriv. Treatment with N2H4 gave 82.7% pure trans-1,2-di-O-palmitoyl-3-O-β-D-galactopyranosyl)-
sn-glycerol, which was characterized spectroscopically.
~0 Citings
374. Pleasant-tasting chewable tablets and their production

By Gaunt, William E.; Gaunt, Marjorie C.
Aq. solns. or aq. alc. solns. of bad-tasting drugs and vitamins are allowed to hydrate rice endosperm at the b.p. of the
soln. In the following drying process, the H2O evap. without migration of the dissolved drugs to the surface. The amt. of
drug that can be absorbed constitutes ∼60% in the final dried product which is then made into chewable tablets wherein
the drugs have a pleasant taste and are readily available upon ingestion. If precooked rice is used, the hydration occurs
at room temp. Absorption of glycerol or propylene glycol (up to 25% of final product) will render the product more pliable
and flexible. Thus, to a soln. of 10 g chlorpheniramine maleate in 120 ml H2O are added 20 g glycerol and 60 g rice
endosperm. The mixt. is heated to the b.p. until all of the soln. is absorbed. After the material is dried at 60-65° and
ground to 30 mesh granules, it is warmed by hot H2O at ∼60°. Molten acetylated monoglyceride (10 g) is added and the
mixt. is allowed to cool with stirring. The product (20 g) is then blended with 400 g of basic granulation mass and
processed into chewable tablets. Similar examples were given for phenylephrine-HCl, dextromethorphan-HBr, glyceryl
guaiacolate, Na butabarbital, betaine-HCl, Na phenobarbital, thiamine mononitrate, and niacinamide.
~1 Citing

375. Odor stabilization of acetylated glycerol fatty acid esters
By Oka, Koji; Wakayama, Eizo; Utsumi, Sakae
Addn. of 0.002% lysine, 0.05% its carbonate, or other amino acids prevented occurrence of acetic odor from the title
esters during storage at 37° for 15-50 days.
~0 Citings
376. Lipids. Synthesis of [cis,cis-1-0-(1,9-octadecadienyl)-sn-glycerol

By Fedorova, G. N.; Serebrennikova, G. A.; Efimova, A. G.; Evstigneeva, R. P.
From Zhurnal Organicheskoi Khimii (1971), 7(5), 957-62. Language: Russian, Database: CAPLUS
The synthesis is described of cis,cis-1-O-(octadeca-1,9-dienyl)-sn-glycerol (I). 3-O-benzyl-sn-glyc) erol was converted in
3 steps (tosylation, acetylation, hydrolysisinto 1-O-benzyl-sn-glycerol (II). The reaction of II with Et2CO3 gave 1-O-
benzyl-sn-glyceryl 2,3-cyclocarbonate which was debenzoylated by catalytic hydrogenation. The transacetalation of sn-
glyceryl 2,3-cyclocarbonate with Me(CH2)7CH:CH(CH2)7CH(OEt)2 gave oleic aldehyde bis(sn-glyceryl 2,3-
cyclocarbonate)acetal (III). The chlorination-dehydrochlorination procedure applied to III gave 2 isomers of 1-O-
(octadeca-1,9-dienyl)-sn-glyceryl 2,3-cyclocarbonate (IV) which was sepd. by chromatog. on silicic acid. The elution of
cis,cis-IV isomer with Et2O from an Al2O3 column removed the cyclocarbonate protective group giving I, which was
identical with the natural lipids degradation product.
~0 Citings
377. Inorganic salt/resin conductive coatings for electrophotographic paper

By Cheng, James K. J.
The moisture retention, moisture sensitivity, cond., and solvent hold-out of electrophotog. papers were improved by
replacing the conductive resin with a mixt. contg. NaCl, NH4Cl, or NaNO3 and a polyhydric alc. Thus, diazo paper was
coated with NaNO3 2.25, poly(vinylpyrrolidone-vinyl acetate) 3.3, poly-(vinyl acetate) 3.45, acetylated starch 2.2,
poly(vinyl alc.) 3.75, glycerol 3, and H2O to 100 parts to give 4.5 lb of coating/3000 ft2 of paper. The paper had a solvent
hold-out of 82 and 79, resp., on the felt and wire sides of the paper. The surface and bulk resistivities of the paper at 20-
80% relative humidity were sufficient for electrophotog. use with wet or dry development.
~1 Citing
378. Identification of glycidyl ethers by paper chromatography

By Ulbrich, Vladimir
From Anal. Fys. Metody Vyzk. Plastu Pryskyric, [Proc. Conf.] (1971), 1, 64-75. Language: Czech, Database: CAPLUS
Monoglycidyl ethers are oxidized with HClO4 to α-alkyl or aryl ethers of glycerol which are sepd. by paper chromatog., or
the glycerol ethers are further oxidized with HIO4 to acetylated derivs. and converted to 2,4-dinitrophenylhydrazones
which are sepd. For glycerol ethers, the paper is impregnated with HCONH2 and DMF; 8:1 C6H6-EtOH is used as
developing solvent; and the spots are detected by spraying with KIO4 and benzidine. For sepn. of phenylhydrazones,
impregnation with DMF or paraffin oil. development with ligroin-C6H14 mixt. satd. with DMF or Me2CO-H2O-DMF, resp.,
and detection by uv irradn. or with SnCl2 and Ehrlich reagent give best results.
~0 Citings
379. Flavor-enhancing compositions for foods and beverages

By Spangler, Herbert D.; Hammes, Paul A.; Everson, Charles W.
A free flowing flavor-enhancing premix. (which mixed with NaCl in a 9:1 diln. without stratification or segregation) was
prepd. comprising NaCl (approx. 50% by wt. of premix), 0.04-4% glycerol or propylene glycol C12-18 fatty acid
monoester (or the acetylated derivs.), and a 12:1 to 50:1 mixt. of monosodium glutamate and 5'-nucleotides. The
preferred 5'-nucleotide was a 50.50 mixt. of the di-Na salts of IMP and GMP.
~6 Citings
380. Effect of wetting cellulose with organic liquids on its reactivity during acetylation
By Sharkov, V. I.; Boiko, T. A.
From Nauchnye Trudy - Leningradskaya Lesotekhnicheskaya Akademiya imeni S. M. Kirova (1971), No. 137, 61-4.
Language: Russian, Database: CAPLUS
The reactivity of cotton cellulose [9004-34-6] to acetylation increased following treatment with ethanol [64-17-5],
methanol [67-56-1], or propanol [71-23-8] at 20.deg. for 24 hr. A smaller increase in reactivity was also obsd. after
cellulose had been treated with ethylene glycol [107-21-1] or glycerol [ 56-81-5 ].
~0 Citings
381. Effect of the degree of acetylation on the enthalpy and entropy of melting of poly(vinyl alcohol) gels and
films
By Verkhotina, L. N.; Gubenkova, E. N.; Gembitskii, L. S.
From Protsessy Strukturoobrazov. Rastvorakh Gelyakh Polim. (1971), 10-17. Language: Russian, Database: CAPLUS
Poly(vinyl alc.) (I) [9002-89-5] samples modified by addn. of various amts. of acetate groups were prepd. and examd. to
study the effect of H bonds on some thermodynamic parameters of I gels and films [m.p. and enthalpy (∆H) and entropy
(∆S) of melting]. The addn. of acetate groups significantly changed intermol. reaction in I and complicated the ordering of
polymer chains. High values of ∆H and ∆S of melting obtained for gels from I-H2O-glycerol and I-H2O-diethylene glycol,
as well as from decrease of poly(vinyl alc.) m.p. by diln. with ethylene glycol are attributed to increased rigidity of mol.
chains in the presence of a poor solvent as compared to pure polymer. The addn. of acetate groups, while increasing
the flexibility of mol. chains, decreased ∆S during transfer from the solid to the liq. state. The transfer from the solid to
the liq. state in the films obtained from aq. solns. is assocd. with the least conformation change of macromols.
~0 Citings
382. Effect of shift-down and growth inhibition on phospholipid metabolism of Escherichia coli
By Ballesta, P. G.; Schaechter, M.
From Journal of Bacteriology (1971), 107(1), 251-8. Language: English, Database: CAPLUS
Phosphatidylethanolamine synthesis apparently is related to growth and cell division, whereas phosphatidylglycerol
metabolism was related to other cell processes in E. coli. Phospholipid synthesis and turnover were not inhibited by
growth-inhibitory amts. of various antibiotics, such as chlortetracycline, and mitomycin. Turnover of phosphatidylglycerol
was inhibited by small amts. of dinitrophenol and by anaerobiosis. Turnover of phosphatidylethanolamine occurred
under conditions of incipient lysis. When cells were shifted down from a rich to a poor medium,
phosphatidylethanolamine synthesis was inhibited, and incorporation of glycerol into the distal position of
phosphatidylglycerol was stimulated. Under these conditions, however, turnover of the phosphate and the acetylated
glycerol moieties of phosphatidylglycerol was inhibited. Increased synthesis of phosphatidylethanolamine was detected
when filamentous cell were induced to make septa.
~0 Citings
383. Crosslinking poly(vinyl alcohol) elastomers

By Matsui, Shigekazu
A N,N'-disubstituted urea, i.e. N,N'-dimethylurea (I) [96-31-1] was used as a crosslinking agent for 10-50:50-90 vinyl
acetate-vinyl alc. copolymer (II) [25213-24-5] to give an elastomer. Thus, 60 parts 35:65 II was mixed with glycerol 20,
triethylene glycol 20, and I 5 parts, and the mixt. was heated 30 min at 140.deg. to give an elastomer having hardness
54, tensile strength 86 kg/cm2, and elongation 560%.
~0 Citings
384. Crosslinking poly(vinyl alcohol) elastomers

Acetylated poly(vinyl alc.) (I) (10-50 mole % acetylated) was crosslinked with aluminum isopropylate (II) [555-31-7] or
titanium isopropylate [13421-84-6] to give an elastomer. Thus, a compn. of 35% acetylated I (mol. wt. 1400) 60, glycerol
20, triethylene glycol 20, and II 10 parts was mill-rolled and heated 30 min at 140.deg. to give an elastomer having
hardness 74, tensile strength 115 kg/cm2, elongation 260%, and resilience 19.
~0 Citings
385. Chromatographic analysis of the alcohol components of alkyd and polyester resins
By Lushchik, V. I.; Zlobina, V. R.; Gomozova, V. G.
The polyol fraction of alkyd and polyester resins was analyzed quant. by aminolysis of the resin with HO(CH2)2NH2 and
acetylation of the free C2-C5 glycols, diethylene glycol, glycerol, trimethylolpropane, and pentaerythritol with Ac2O; the
resulting polyol acetates were analyzed with <10% error by gas-liq. chromatog. using 5% polyethylene glycol adipate on
Chromosorb at 100-220° with N carrier and a flame ionization detector.
~0 Citings
386. Alkyl acyl ethanolamine glycerophosphatides in rat intestinal mucosa

By Yurkowski, Michael; Walker, Brian Lawrence
DOI:10.1016/0009-3084(71)90032-6
The ethanolamine glycerophosphatides (EGP) were isolated from rat mucosal lipids by column and thin-layer chromatog.
and found to contain alkyl acyl EGP. After hydrolysis and acetylation, the resulting alkyl diacetyl glycerols were sepd. by
gas-liq. chromatog. and the paraffinic moieties were shown to consist of C18- and C20-satd. and C18-monounsatd.
residues. The fatty acid compns. of the 1,2-diacyl glycerols and 1-alkyl-2 acyl glycerols obtained by treatment of the
phosphatides with phospholipase C were detd. The 1-alkyl-2 acyl glycerols were rich in polyunsatd. acyl residues.
~0 Citings
387. Activation of mercerized cellulose with polyhydric alcohols to raise its reaction capability during acetylation
By Sharkov, V. I.; Fedotov, Yu. M.
From Nauch. Tr., Leningrad. Lesotekh. Akad. (1971), No. 137, 45-9. Language: Russian, Database: CAPLUS
Cellulose [9004-34-6] was treated after mercerization with 1-10% aq. solns. of glycols or glycerol [ 56-81-5 ] to improve
its reactivity in acetylation, giving reactivity which increased with increasing alc. concn. and was somewhat lower than
that of the original cellulose. Hexamethylene glycol [629-11-8] and tetramethylene glycol [110-63-4] had the greatest
activating effect. Tetraethylene glycol [112-60-7], pentaethylene glycol [4792-15-8], hexaethylene glycol [2615-15-8],
heptaethylene glycol [5617-32-3], and octaethylene glycol [5117-19-1] had approx. equal activation effects.
~0 Citings

388. Activation of cotton cellulose with polyhydric alcohols to increase its acetylation reactivity
By Sharkov, V. I.; Dmitrieva, O. A.; Fedotov, Yu. M.; Molodova, T. P.
From Nauch. Tr., Leningrad. Lesotekh. Akad. (1971), No. 137, 40-5. Language: Russian, Database: CAPLUS
Pre-dried cellulose [9004-34-6] was treated with water or acetone solns. of glycols or glycerol [ 56-81-5 ], increasing its
reactivity in acetylation. Hexamethylene glycol [629-11-8] and tetramethylene glycol [110-63-4] had the largest activating
effects. Ethylene glycol [107-21-1], diethylene glycol [111-46-6], triethylene glycol [112-27-6], 1,3-butylene glycol [107-
88-0], and polypropylene glycol [25322-69-4] were also used.
~0 Citings
389. Ruminal bacterial degradation of benzo(b)-thien-4-yl methylcarbamate (Mobam) and effect of Mobam on
ruminal bacteria
By Williams P P; Stolzenberg R L
From Applied microbiology (1972), 23(4), 745-9, Language: English, Database: MEDLINE
Mixtures of ruminal bacteria degraded benzo(b)thien-4-yl methylcarbamate (Mobam) to 4-hydroxybenzothiophene,
CO(2), and polar product(s). The metabolite, 4-hydroxybenzothiophene, was identified (after acetylation) by
comparative infrared and mass spectrometry with an authentic sample. Carbon dioxide and polar product(s) were
produced by degradation of the methylcarbamate moiety. Ten previously characterized strains of ruminal bacteria with
diverse physiological capabilities did not degrade Mobam. However, three tributyrin-hydrolyzing strains were isolated
that did degrade Mobam. Mobam inhibited growth of two of ten strains isolated on Mobam-free glycerol-tributyrin
enrichment medium. One of these strains was also sensitive to 2-carbomethoxy-propene-2yl dimethyl phosphate
(Phosdrin). Mobam prevented some ruminal bacteria from producing zones of hydrolysis in tributyrin emulsion media
and inhibited some ruminal bacteria from degrading 1-naphthyl acetate and fluorescein-3',6'-diacetate.
~1 Citing
390. Possible relation between phosphoinositides and the diglyceride pool in rat brain
By Keough, K. M. W.; MacDonald, G.; Thompson, W.
Database: CAPLUS, DOI:10.1016/0005-2760(72)90198-1
Ox brain triphosphoinositide (tri-I) was incubated with a solubilized prepn. of ox brain I phosphodiesterase and at different
time intervals the fatty acid compns. of the hydrolysis product, diglyceride, and the residual substrate were examd. The
fatty acid compns. of both fractions at all times were essentially const. indicating no high degree of selectivity of particular
mol. species of tri-I by the enzyme. Since the liberated diglycerides largely reflected the original compn. of I hydrolysis
was 1-stearoyl-2-arachidonoyl-sn-glycerol (II). Mono-, di- and tri-Is from rat brain were rich in stearate and arachidonate,
which were in equimolar proportions and accounted for ∼80% of the total fatty acids. Similarly, the total diglycerides of
rat brain contained ∼30% each of sterate and arachidonate, while, in contrast, mono- and triglycerides had very little
arachidonate. The rat brain diglycerides were acetylated and sepd. and quantitated by argentation-thin-layer chromatog.
and gas-liq. chromatog. The tetraene species greatly predominated and consisted largely of stearate paired with
arachidonate. Hydrolysis of rat brain diglycerides with pancreatic lipase showed that arachidonate was located in the 2-
position and stearate mostly in the (3)-position. The diglycerides were converted to phosphatidylphenols, which were
hydrolyzed with snake venom phospholipase A2. About 90% of the phosphatidylphenols were converted to
lysophosphatidylphenols and all the arachidonate was liberated as free fatty acid. The collective evidence suggests that
almost all the brain diglyceride is 1,2-diacyl-sn-glycerol and that II accounts for ∼60% of this fraction. The possibility is
raised that the pool of arachidonoyl diglyceride in brain may be derived, in part, from hydrolysis of Is by the
phosphodiesterase.
~2 Citings
391. Oviposition pheromone of the mosquito Culex tarsalis. Diglyceride composition of the active fraction
By Starratt, Alvin N.; Osgood, Charles E.
Database: CAPLUS, DOI:10.1016/0005-2760(72)90224-X
An egg-assocd. oviposition pheromone of the mosquito C. tarsalis was investigated and an active fraction obtained
chromatog. from the crude ext. It consisted of a mixt. of 1,3-diglycerides and yielded Me esters of mono-and dihydroxy
fatty acids on acid-catalyzed methanolysis. The major monohydroxy acids were 3-hydroxytetradecanoic acid, 3-
hydroxyhexadecanoic acid, and 3-hydroxyoctadec-cis-11-enoic acid while the major dihydroxy acid was erythro-5,6-
dihydroxyhexadecanoic acid. In the diglycerides, the fatty acid OH groups were acetylated. It is proposed that the
monohydroxy acid residues were esterified with 1 of the α-positions of the glycerol moiety and the dihydroxy acid
residues with the other.
~4 Citings
392. Industrial soaps for removing grease and oil from skin
By Martineau, Jean; Biechler, Francois Joseph
From Fr. (1972), FR 2082473 A5 19711210, Language: French, Database: CAPLUS
Fatty acid amides, e.g. diethanolamine-2-ethanolstearylamide complex (I) [35894-83-8] and copra acid diethanolamide-
diethanolamine complex (II), were used in the prepn. of industrial hygiene soap which did not hurt the skin. Thus, 207 g
copra acid was heated at 160.deg. with 210 g diethanolamine to give II. A liq. soap compn. was prepd. comprising Na
laurylsulfonate 20, glycerol 1.5, acetylated lanolin 2.5, water 50, I 25, and perfume 1 kg.
~1 Citing
393. Glycosyl diglycerides. III. Synthesis of unsaturated mannosyl diglyceride

By Bashkatova, A. I.; Senyushkina, N. N.; Shvets, V. I.; Evstigneeva, R. P.
Treatment of [RCO2CH2CH(CH2OH)O]2CH2 (R = C15H31) with the mannose orthoacetate (I) gave 43.8% 2,2'-O-
methylenebis[1-O-palmitoyl-3-O-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)]-sn-glycerol, which was heated with AcOH-
MeOH to yield 85.3% mannosylglyceride II (R = H, R1 = C15H31). Acylation of the latter with oleoyl chloride gave 95.3%
glyceride II (R = C17H33, R1 = C15H31). Analogously obtained was 93% glyceride II (R = R1 = C15H31) (III).
Treatment of deacetylated III with NaOH yielded 96% 3-O-α-D-mannopyranosyl-sn-glycerol (IV), which was acetylated by
AcCl to give 96.5% of the hexaacetate.
~0 Citings
394. Gas-liquid chromatography of alditol acetates

By Sloneker, J. H.
From Methods in Carbohydrate Chemistry (1972), 6, 20-4. Language: English, Database: CAPLUS
Aldoses are reduced with borohydride to the corresponding alditols which are then acetylated and sepd. by gas
chromatog. Conditions are given for the acetates of the following alditols: glycerol, erythritol, 2-deoxyribitol, rhamnitol,
fucitol, ribitol, arabinitol, xylitol, 2-deoxyglucitol, mannitol, galactitol, and glucitol.
~38 Citings
395. Determination of hydroxyl group content in lacquer resins based on terephthalate polyesters
By Majewska, Feliksa; Glinka, Zdzislawa
From Polimery (Warsaw, Poland) (1972), 17(5), 265-6. Language: Polish, Database: CAPLUS
The acetylation of Poles 200/95 [glycerol-modified poly(ethylene terephthalate)] (I) with Ac2O in 350:100 tetrahydrofuran-
pyridine mixt., followed by the alkalimetric detn. of the residual AcOH provided a method for the OH group detn. in I. The
method can be used in the process control labs.
~0 Citings

396. Delustering fabrics containing acetylated cellulose fibers
From Fr. Demande (1972), FR 2113773 A5 19720630, Language: French, Database: CAPLUS
Cellulose acetate textiles were delustered without loss of tear strength and elongation, or change of hand, by application
of a paste contg. a hygroscopic material, a mineral or aliph. carboxylic acid, and a thickener. Cellulose diacetate taffeta
degreased in an aq. soln. of poly(oxyethylene) alkylphenol ether, sulfuric acid ester, and higher alc. was treated with a
paste contg. 30% aq. corn starch soln. 35, 45% aq. Nafkacrystal gum soln. 25, formic acid [64-18-6] 20, glycerin (I) [ 56-
81-5 ] 5, and H2O 15 parts to give a fabric with relative luster 74.9, elongation 46.6%, and tear resistance 0.91 kg
compared with values of 81.6, 35.8%, and 1.05 kg using a paste without the acid and I. Pastes contg. other starches and
gums with e.g. phosphoric acid [7664-38-2], butyric acid [107-92-6], maleic acid [110-16-7], sulfuric acid [7664-93-9],
triethanolanine [102-71-6], urea [57-13-6], and ethylene glycols were also used.
~0 Citings
397. Crosslinking of thermosetting poly(vinyl alcohol) elastomers

A sheet of 10-50 mole % acetylated poly(vinyl alc.) (I) with crosslinking agents was wound into a hose or a roll, covered
with a poly(vinylidene chloride) (II) [9002-85-1] film, and vulcanized in steam. Thus, a compn. of 35 mole % acetylated I
60, glycerol 20, triethylene glycol 20, trimethylolmelamine 10, and Sumitex ACX (an accelerator) 1 part was calendered
into a 1-mm .tim. 30-cm sheet. The sheet was wound on an iron roll core to 2 cm. The roll was covered with several
plies of II tape, heated 10 min at 80.deg., and steamed 70 min at 140.deg. to give a vulcanizate without bubbles.
~0 Citings
398. Analytical determination of polypropylene glycols and glycerol in plasticizing baths during manufacture of
viscose films
By Pikala, M.
From Chemicke Vlakna (1972), 22(2), 21-8. Language: Slovak, Database: CAPLUS
The dichromate, periodate, and acetylation methods used for the detn. of mono- and dipropylene glycol [25265-71-8],
and glycerol [ 56-81-5 ] singly or simultaneously were evaluated; the procedures were simplified considerably for use in
the anal. control of the viscose film plasticizer baths.
~0 Citings
399. Analysis of polyesters

By Sestrienkova, M.; Singliar, M.
From Petrochemia (1972), 12(4), 94-7. Language: Slovak, Database: CAPLUS
The order of glycerol [ 56-81-5 ] liberating efficiency was ethanolamine (I) [141-43-5] > 2-phenylethylamine [64-04-0] >
butylamine [109-73-9] in an evaluation of amine alternatives for alkyd resin aminolysis (ASTM D-2456-69 method A) to
identify polyols in polyesters. The liberated polyols were acetylated with Ac2O, picked up in CHCl3, and analyzed by gas
chromatog., with the Ac2O peak interference in some cases. Acetylation of diethylene glycol [111-46-6] and
trimethylolpropane (II) [77-99-6] was incomplete since some Ac2O acetylated I, e.g. giving mono-, di-, and triacetates of
II. When the method was modified by boiling the acetylated mixt. with water to hydrolyze the Ac2O before CHCl3 extn.,
some acetates were lost. Therefore, the alternative amines were useful for quant. anal. when the unknown and
calibration procedures were identical.
~0 Citings
400. 5-(Aminoalkylamino)-6 (or 7) -halo-8-quinolinemethanols, their alkyl ethers and alkanoyl esters
By Archer, Sydney; Bailey, Denis M.
The title compds. (I, R = Me, Et, hexyl, Ac, EtCO, PrCO, HCO; R1, R2 = H, C2-6 alkyl or NR1R2 = N-heterocycle; X =
halo; n = 2-4), schistosomacides in hamsters and mice at 0.5-100 mg/kg, were prepd. Thus, in the last step of synthesis
Me 6-chloro-5-(2-diethylaminoethyl-amino)-8-quinolinecarboxylate was reduced with LiAlH4 to give the
quinolinemethanol (I, R = H; R1 = R2 = Et, X = 6-Cl, n = 2), which was methylated to the Me ether by p-
MeC6H4SO3HMeOH and acetylated to the acetate ester by Ac2O.
~0 Citings
401. Transport of sugars and amino acids in bacteria. VII. Characterization of the reaction of restoration of active
transport mediated by binding protein
By Anraku Y; Kobayashi H; Amanuma H; Yamaguchi A
From Journal of biochemistry (1973), 74(6), 1249-61, Language: English, Database: MEDLINE
~4 Citings
402. Reduction of α-D-hexopyranosulosides

By Lemieux, R. U.; James, K.; Nagabhushan, T. L.
From Canadian Journal of Chemistry (1973), 51(1), 27-32. Language: English, Database: CAPLUS, DOI:10.1139/v73-
004
Redn. of Me2CH tri-O-acetyl-α-D-arabino-hexo-pyranosuloside with NaBH4 or B2H6 leads almost exclusively to the
gluco-configuration. Catalytic redns., on the other hand, provide an epimeric mixt. with the manno-configuration
predominating in ratios of 2:1. The redn. of Me26cH tri-O-acetyl-α-d-lyxo-hexopyranosuloside with either NaBH4 or
B2H6 is less stereo-selective than in the case of the arabino-isomer and leads to compds. of the galacto- and
taloconfigurations in the ratio of 3:2. The latter is formed highly stereoselectively when the lyxosuloside deriv. is
hydrogenated catalytically. 2.0-(α-D-Mannopyranosyl)glycerol the gluco-isomer are synthesized.
~8 Citings
403. Proteolytic enzymes of the K-1 strain of Streptomyces griseus obtained from a commercial preparation
(pronase). IV. Structure-function studies of the two smallest serine endopeptidases. Stabilization by glycerol
during reaction with acetic anhydride
By Siegel, Steven; Awad, William M., Jr.
From Journal of Biological Chemistry (1973), 248(9), 3233-40. Language: English, Database: CAPLUS
A study was carried out on some of the properties of the 2 smallest serine endopeptidases from Pronase which were
previously purified to homogeneity. Each enzyme was homologous with bovine chymotrypsin and had isoleucine as the
N-terminal residue. The smaller enzyme is free of lysine, whereas the larger enzyme contains only 1 lysine residue.
Reaction of the larger enzyme with Ac2O yielded a homogeneous, active, and stable derivative, as indicated by ion
exchange chromatography and acrylamide gel electrophoresis. Reaction of the smaller enzyme with Ac2O yielded 2
chromatographic components, of which only the larger demonstrated activity against Nα-acetyl-L-tyrosine Et ester. This
active component autolyzes during acrylamide gel electrophoresis but appears as a single band by cellulose acetate
electrophoresis. The excellent yields of these protein derivatives were only achieved by modifying the past standard
techniques of acetylation. In each reaction mixture glycerol was included at a concentration of 20% by volume. As a
result only small amounts of native proteins were required to prepare the derivatives. Analysis of each enzyme revealed
complete acetylation of the N-terminal isoleucine residue. Acetylation resulted in only modest changes in the Km and
Vmax of each enzyme with N-acetyl-L-tyrosine Et ester as substrate. Despite the earlier observation that only the larger
enzyme demonstrated marked stability in 6M guanidinium chloride, there was no difference in the heat stabilities of the 2
enzymes. Metal-free enzyme was prepared in each case by gel filtration at a low pH in the absence of metals. These
metal-free proteins demonstrated the same temperature stabilities as the EDTA-treated native enzymes. On the many
cations tested, Ca2+ was specific in each case in restoring the stability at higher temperatures to the metal-free
enzymes.
~2 Citings

404. Oxidation and low-temperature-resistant glycerides of natural fatty acids
By Bueinger, Heinrich; Renckhoff, Gustav
Dodecanoyl- (I) and tetradecanoyldiacetylglycerol, resistant to oxidn. and crystn. at low temps., were prepd. by
acetylation of dodecanoyl and tetradecanoyl glycerides. I also inhibited the oxidn. and crystn. of other glycerides.
~0 Citings
405. Monoglyceride esters of diacetyltartaric acid

From Span. (1973), ES 389172 A1 19730601, Language: Spanish, Database: CAPLUS
The glyceride, RCO2CH2CH(OH)CH2O2CCH(OAc)CH(OAc)CO2H, which was used as an emulsifier in the baking
industry, was prepd. by esterifying tartaric acid with Ac2O and then with the com. monoglyceride contg. ∼50%
monoglycerides. The product had an acid no. of 71.5 and a sapon. no. of 395.
~0 Citings
406. Liquid glycerides

By Buenger, Heinrich; Renckhoff, Gustav
From Brit. (1973), GB 1339795 A 19731205, Language: English, Database: CAPLUS
Oxidn.-resistant liq. glycerides, for use in the pharmaceutical, cosmetic, and food industries, which did not give soapy
smelling fatty acids by cleavage or cryst. deposits after storage at 0.deg. comprised diacetyl monododecanoyl glyceride
(I) [30899-62-8] substantially free of other glycerides or mixts. contg. 15-78% I and diacetyl hexadecanoyl glyceride
[41229-14-5] and/or diacetyl tetradecanoyl glyceride [41229-15-6]. Thus, a mixt. of 90.5 wt. % monododecanoyl glycerol
[27215-38-9] and didodecanoyl glyercol [27638-00-2], obtained by mol. distn. of lauric acid partial glyceride, was
acetylated using Ac2O to give a product with hydroxy, sapon., and acid nos. 0, 462, and 2.35, resp. which remained clear
after storage 1 week at 0.deg..
~0 Citings
407. Formula modifications in a solvent-free tablet film coat

By Tuerck, Paul A.; Mc Vean, Duncan E.
From Journal of Pharmaceutical Sciences (1973), 62(9), 1534-7. Language: English, Database: CAPLUS,
DOI:10.1002/jps.2600620935
Solvent-free formulations suitable for use as film coatings are described. Coatings are applied by spraying molten mixts.
onto tablets in a conventional coating pan. The effects of a series of 17 additives on 2 representative basic formulations
are evaluated. Results are presented relative to appearance, disintegration, friability, and uniformity. Desirable
characteristics imparted by the additives may be easily selected from tables and used in the formulation of subsequent
coating compns. The concn. of shellac in the basic formulations was found to govern the rapidity of disintegration of the
coatings regardless of additives. Of the additives evaluated, only castor oil, cocoa butter, and iso-Pr myristate improved
the basic formulations.
~3 Citings
408. Cyanoacetylated polyamine azo couplers

By Muller, Peter
Diazo reprodn. compns. contg. cyanoacetylated polyamine couplers such as N1,N3-di(cyanoacetyl)diethylenetriamine
hydrochloride, N1,N5-di(cyanoacetyl)tetraethylenepentamine hydrochloride, 1-cyanoacetyl)-4β-hydroxyethylpiperazine,
N1, N4-di-(cyanoacetyl)triethylenetetramine hydrochloride (I), and 1-cyanoacetyl-4-cyanoacetamidoethylpiperazine which
are non-volatile, heat stable under all conditions to which diazo reprodn. materials are subjected, and which do not tend
to migrate from the sensitized diazo layer into the support sheet are described. Thus, a precoated paper support was
overcoated with a compn. contg. sulfosalicylic acid 10, citric acid 10, caffeine 20, β-hydroxynaphthoic acid
morpholinopropylamide 5, I 18, 1-diazo-2,5-diethoxy-4-morpholinobenzene chloride 1/2 ZnCl2 12, saponin 1, ZnCl2 40 g,
glycerin 20 ml, and H2O to 1 l., dried, imagewise exposed, and developed in a hot NH3 developing section of a com.
processor to give an image of uniform black and gray shades. Nonexposed paper after storage at 50° and 75% relative
humidity showed neither precoupling nor any color shift.
~0 Citings
409. Composition of the hydroxy acid-lactone part of soluble wood resin

By Shirokova, M. N.; Krutov, S. M.; Sorokin, I. S.; Kirova, S. M.
From Gidroliznaya i Lesokhimicheskaya Promyshlennost (1973), (5), 18-20. Language: Russian, Database: CAPLUS
The water-sol. fraction of wood resins, a byproduct of rosin manuf., contains hydroxyacids. A procedure was developed
for converting these hydroxyacids to diol and triol acetates and identifying the latter by gas chromatog. The sol. fraction
was 1st acetylated with Ac2O in the presence of Mg(ClO4)2, the acetoxyalc. mixt was reduced with LiAlH4, and the redn.
products were acetylated in situ to liq. acetates b2 40-180.deg.. The chromatog. of this fraction on a column filled with
Cellite contg. 20% neopentyl glycol succinate at 170.deg. with 50 ml/min H flow gave 16 compds. of which 12 were
identified as 1,2-propylene diacetate [623-84-7], ethylene diacetate [111-55-7], 1,2-butylene diacetate [13814-27-2], 1,3-
butylene diacetate [1117-31-3], 1,3-propylene diacetate [628-66-0], 1,4-pentanediol diacetate [32864-71-4], 1,6-
hexanediol diacetate [6222-17-9], glycerol triacetate [102-76-1], 1,2,4-butanetriol triacetate [14835-47-3], and 1,2,5-
pentanetriol triacetate [5470-86-0].
~0 Citings
410. Analysis of the products of Smith degradation of polysaccharides by glc [gas-liquid-chromatography] of the
acetylated, derived aldononitriles and alditols
By Baird, J. K.; Holyroyde, M. J.; Ellwood, D. C.
From Carbohydrate Research (1973), 27(2), 464-7. Language: English, Database: CAPLUS, DOI:10.1016/S0008-
6215(00)81329-4
Oxidn. of polysaccharides with excess aq. NaIO4, subsequent redn., dialysis, hydrolysis of non-diffusible material with M
H2SO4 at 100°, oximation of resultant sugars, followed by treatment with Ac2O, gave mixts. of acetylated alditols and
aldononitriles separable by gas-liq. chromatog. Quant. ratios of products formed allowed detn. of chain lengths of
polysaccharides, as demonstrated with glycogen, amylopectin, and laminaran.
~6 Citings
411. Use of (1-14C) aectic anhydride to quantitate diglycerides: a new analytical procedure
By Banschbach M W; Geison R L; O'Brien J F
From Analytical biochemistry (1974), 59(2), 617-27, Language: English, Database: MEDLINE
~13 Citings
412. Two-year feeding and multigeneration studies in rats on five chemically modified starches
By De Groot, A. P.; Til, H. P.; Feron, V. J.; Dreef-Van der Meulen, Harriet C.; Willems, Marian I.
From Food and Cosmetics Toxicology (1974), 12(5-6), 651-63. Language: English, Database: CAPLUS,
DOI:10.1016/0015-6264(74)90236-3
Five chem. modified starches, acetylated distarch phosphate, acetylated diamylopectin phosphate, starch acetate,
hydroxypropyl distarch glycerol and phosphated distarch phosphate were fed to rats at dietary levels of 0 (control), 5, 10,
and 30% for 2 years, and at one level, 10%, over 3 generations. In the 2-year study, no adverse effects were obsd. on
mortality, food intake, hematol. blood biochem., or urine compn. Each of the modified starches, except the phosphated
distarch phosphate, slightly reduced body wts. at the 30% level and caused distinct cecal enlargement at 10 and 30% but
the microscopic structure of the cecal wall was normal. In comparison with the controls, the males fed the 30% level of
any of the modified starches showed a slightly increased degree and incidence of focal hyperplasia of the renal papillary
and pelvic epithelium, accompanied by calcified patches in the underlying tissue. The studies did not provide any
indication of carcinogenicity. The multigeneration study showed no effect on fertility, on lactation performance, or on
embryonic or preweaning mortality. Extensive microscopic examn. of the third-generation rats failed to reveal any
changes attributable to treatment. Feeding of each of the modified starches at dietary levels up to 30% for 2 years and at
a level of 10% over 3 generations did not result in any distinct effect of toxicol. significance.
~10 Citings
413. Synthesis of two disaccharides, of partially O-acetylated 3,6-dideoxyglycosides and degradation studies of
some hexodialdopyranosides
By Beving, Hakan
From Chemical Communications (Stockholm University) (1974), (11), 38 pp.. Language: English, Database: CAPLUS
The synthesis of 1-O-β-D-galactofuranosyl-D-glyceritol, umbilicin, and acetylated Me α-and β-abequosides as well as the
title degrdn. studies were reviewed with 47 refs.
~0 Citings
414. Proteolytic enzymes of the K-1 strain of Streptomyces griseus obtained from a commercial preparation
(pronase). VII. Acetylation of pronase trypsin
By Awad, William M., Jr.; Ochoa, Maria S.
CAPLUS, DOI:10.1016/S0006-291X(74)80012-4
Reaction of Pronase trypsin with Ac2O yielded a homogeneous, active, and stable deriv. This was achieved by including
glycerol in the acetylation reaction as previously described (Siegel, S., Awad, W. M., Jr., 1973). Acetylation resulted in
no change in Km and only a moderate decrease in Vmax with Nα-benzoyl-L-arginine-p-nitroanilide as substrate. As with
bovine trypsin the single N-terminal residue was not acetylated. This is in contrast to the other homologous mammalian
and microbial enzymes where complete acetylation of N-terminal residues are noted. Thus, a close conformational
homology is suggested around the N-termini of the microbial and mammalian trypsins.
~0 Citings
415. Oil-based coating composition

By Rose, Henry J.
Artificial sausage casings, such as casings of regenerated cellulose (clear cellulose and fibrous-reinforced types), are
peeled much more easily from sausages processed in the casing when coated on the inner surface with an oil-based
compn. consisting of a food grade mineral oil mixed with an acetylated fatty monoglyceride and 5-30% of an alkoxylated
type surfactant which is poorly sol. in mineral oil. The compn. is applied to the inner surface of the casing during shirring
at 0.0001-1.0%, preferably 0.2-0.6%, of the casing wt. Thus, a coating compn. was prepd. consisting of food grade
mineral oil (N.F. No. 9) 40, acetylated glycerol monooleate (Myvacet 9-45) 40, and polyethylene glycol (400)
monostearate 20%. When this compn. was used at 0.5% on the internal side of frankfurter clear cellulose casings, these
casings had 20-100% fewer peeling misses, using a com. casing peeler, as compared with untreated controls or with
controls contg. only an internal coating of mineral oil or an acetylated monoglyceride. The frankfurters were almost
totally free of fat pockets or surface mottling which occurred with control casing or other release coatings.
~2 Citings

416. Identification of triacetin and other acetic esters in cellulose triacetate cigarette filters
By Constantinescu, Titus
From Industria Alimentara (Bucharest) (1974), 25(4), 199-201. Language: Romanian, Database: CAPLUS
Glycerol and glyceryl mono-, di-, and triacetates were detd. qual. by thin-layer chromatog. in the EtOH ext. of cigarette
filters. The ext. was obtained by refluxing the cigarette filter with EtOH, cooling the liq., filtering, and then centrifugation.
The identification was done by comparison with std. compds. and confirmed by chem. reactions (acetylation, sapon.)
done directly on the plate, followed by thin-layer sepn. of the reaction products.
~0 Citings
417. Experimental pantothenic acid deficiency in the rat

By Pietrzik K; Hesse C; Schulze zur Wiesch E; Hotzel D
From Die Nahrung (1974), 18(5), 491-502, Language: German, Database: MEDLINE
~0 Citings
418. Easily peelable sausage casing

By Rose, Henry J.
Sausages such as frankfurters and bolognas formed in synthetic casings are more easily peeled when the inside of the
casings is coated with a food grade mineral oil mixed with an acetylated fatty monoglyceride and 5-30% of an alkoxylated
type surfactant which is only slightly sol. in the mineral oil. For example, food grade mineral oil 40, acetylated glycerol
monooleate (Myvacet 9-45) 40, and polyethylene glycol (400) monostearate 20% were mixed and introduced at 0.5% of
the wt. of the casing through the mandrel of the shirring machine while clear regenerated cellulose casing was being
shirred. The coated casing was then stuffed with frankfurter emulsion, linked, smoked, and cooked. These casings had
20-100% fewer peeling misses with a com. casing peeler than did untreated controls.
~5 Citings
419. Digestibility of acetylated distrach glycerol--effect on growth, serum biochemical values and body
composition of Pitman-Moore miniature pigs
By Anderson T A; Filer L J Jr; Fomon S J; Andersen D W; Jensen R L; Rogers R R
From Food and cosmetics toxicology (1974), 12(2), 201-7, Language: English, Database: MEDLINE
~0 Citings
420. Digestibility of acetylated distarch glycerol. Effect on growth, serum biochemical values, and body
composition of Pitman-Moore miniature pigs
By Anderson, T. A.; Filer, L. J., Jr.; Fomon, S. J.; Andersen, D. W.; Jensen, R. L.; Rogers, R. R.
From Food and Cosmetics Toxicology (1974), 12(2), 201-7. Language: English, Database: CAPLUS,
DOI:10.1016/0015-6264(74)90365-4
Two groups each of eight Pitman-Moore miniature pigs were weaned at 3 days of age and then, for 25 days, were
allowed unrestricted access to formula diets identical except for the type of carbohydrate. The diets contained 6% of
thin-boiling waxy corn starch or acetylated distarch glycerol. At 14 and 21 days of age, the body wt. of pigs fed the
control starch diet was significantly higher, while at 28 days, the wt. of the empty cecum and the water content of the wet
carcass and fat-free wet liver were significantly lower and the carcass-fat and liver-protein contents were significantly
greater than the corresponding values for pigs fed the diet contg. acetylated distarch glycerol as the sole carbohydrate.
~0 Citings
421. Determination of humectants in tobacco

By Viart, Pierre
From Annales du Tabac, Section 1 (1974), 12, 89-97. Language: French, Database: CAPLUS
A gas chromatog. method for detg. propylene, butylene, diethylene, and triethylene glycols, glycerol and sorbitol in
tobacco is described. The tobacco is first extd. with water and the water removed by distn. with pyridine. The polyols are
acetylated and the Ac derivs. are analyzed in the gas chromatograph under conditions varying according to which
compd. is being detd.
~0 Citings
422. Chromatographic analysis of alcoholic components of alkyd and polyester resins

By Lushchik, V. I.; Zlobina, V. R.; Gomozova, V. G.
Alcs. (13) present in some parts of the title resins were detd. as acetates by chromatog. without interference of peaks of
acetylated amines. The sample, contg. 1,4-butanediol or pentaerythritol internal std., was treated with
polyethylenepolyamine and acetic anhydride. The reaction products were separated by chromatog. of silicone resin E-
301 supported on chromosorb. The alcs. included ethylene glycol [107-21-1], N-phenyldiethylolamine [120-07-0], etc.
Pentaerythritol detn. was <5%.
~0 Citings
423. Acetylation of pronase trypsin

By Awad W M Jr; Ochoa M S
From Biochemical and biophysical research communications (1974), 59(2), 527-34, Language: English, Database:
MEDLINE
~0 Citings
424. Acetylation of cellulosic materials

By Jain, Shishir K.
From Indian (1974), IN 131528 19740727, Language: English, Database: CAPLUS
Cellulose fibers impregnated with acetylation catalysts were blended with cellulosic or synthetic fibers and acetylated by
exposure to Ac2O [108-24-7] vapor or by spraying with liq. Ac2O. Thus, viscose fibers were impregnated with an aq.
soln. contg. NaOAc [127-09-3] and glycerol, squeezed to provide NaOAc and glycerol content of 14.7 and 1.2% resp.,
dried to 10-11% moisture content, and blended with 4 times their wt. of viscose fibers. The blended fiber was dried to a
3-4% moisture content, exposed to Ac2O vapors at 135-40° for 0.5 hr to give cellulose acetate fibers of 53.9% HOAc
content.
~0 Citings
425. The proteolytic enzymes of the K-1 strain of Streptomyces griseus obtained from a commercial preparation
(Pronase). Specificity and immobilization of aminopeptidase
By Vosbeck K D; Greenberg B D; Awad W M Jr
From The Journal of biological chemistry (1975), 250(10), 3981-7, Language: English, Database: MEDLINE
We recently described the purification of two aminopeptidases from Streptomyces griseus (Vosbeck, K.D., Chow, K.-
F., and Awad, W.M., Jr. (1973) J. Biol. Chem. 248, 6329-6034). An analysis of the amino acid composition reveals
very little differences in the two proteins. Each protein has alanine as the NH2-terminal residue. The aminopeptidases
were treated separately with acetic anhydride; as noted in the past, the presence of glycerol is required to achieve
excellent yields of acetylated active derivatives (Siegel, S., and Awad, W.M., Jr. (1973 J. Biol. Chem. 248, 3233-
3240). However, in the present case much higher concentrations of glycerol (50%) are needed during acetylation to
obtain derivatives with completely reacted NH2-terminal residues. The epsilon-amino groups were not completely
acetylated. In contrast to the native enzymes, the acetylated derivatives show an affinity for DEAE-cellulose, a
property consonant with the changes in net charge. The kinetic constants for each enzyme against L-leucine-p-
nitroanilide do not change significantly after acetylation. The specificities of the two aminopeptidases were examined
extensively on a semiquantitative basis. The activities are not restricted by the length of substrate chains. Each
enzyme shows a preference for hydrophobic residues at the ultimate and penultimate positions. Charge residues are
released a slower rates. No prolidase activity is demonstrable even at high enzyme to substrate ratios; however, NH2-
terminal proline residues are released readily. D-Amino acid residues at the ultimate or penultimate position
substantially reduce the rate of hydrolysis; D-leucyl-D-leucine is not hydrolyzed...
~2 Citings
426. Synthesis of unsaturated mixed acid phosphoinositides

By Shevchenko, V. P.; Tsirenina, M. L.; Molotkovskii, Yu. G.; Bergel'son, L. D.
From Doklady Akademii Nauk SSSR (1975), 223(2), 504-6 [Biochem]. Language: Russian, Database: CAPLUS
Phosphoinositides (I, R = PO3H2, H) were prepd. in 12 steps from di-O-cyclohexylidenemyoinositol (II).
~0 Citings
427. Synthesis of 3-O-(α-D- and β-D-mannopyranosyl)-sn-glycerols

By Kaplun, A. P.; Kalugin, V. E.; Shvets, V. I.; Evstigneeva, R. P.
From Trudy Instituta - Moskovskii Institut Tonkoi Khimicheskoi Tekhnologii imeni M. V. Lomonosova (1975), 5(1), 57-9.
Language: Russian, Database: CAPLUS
Treatment of mannopyranosyl bromide I with 1,2-di-O-benzyl-sn-glycerol (II) by the Koenigs-Knorr synthesis gave a mixt.
contg. 45% III (R = Ac, R1 = PhCH2) and 10% IV (R = Ac, R1 = PhCH2). Similarly, orthoester V treated with II gave 87%
of a mixt. contg. III, IV (R = Ac, R1 = PhCH2). Hydrogenolysis of the mixt. gave 68% III (R = Ac, R1 = H) and 10% IV (R
= Ac, R1 = H). Addnl. obtained were III, IV (R = R1 = Ac, H).
~0 Citings
428. Synthesis of 3-O(α-D- and β-D-mannopyranosyl)-sn-glycerols

By Kaplin, A. P.; Kalugin, V. E.; Shvets, V. I.; Evstigneeva, R. P.
From Tr. Mosk. In-ta Tonkoi Khim. Tekhnol. (1975), 5(1), 57-9. Language: Russian, Database: CAPLUS
Title only translated.
~0 Citings
429. Polymer compositions for chewing gum

By Tezuka, Shichigoro; Seno, Tadashi; Yokoyama, Takehiko
From Jpn. Kokai Tokkyo Koho (1975), JP 50062290 A 19750528, Language: Japanese, Database: CAPLUS
The compns. comprised poly(vinyl acetate) (I) [9003-20-7] and acetylated esters of fatty acids and glycerin [ 56-81-5 ],
propylene glycol [57-55-6], or sugar [57-50-1]. Thus, a mixt. of vinyl acetate 100, EtOH 10, an acetylated monoglyceride
(a plasticizer) 60, and Bz2O2 0.2 part was heated at reflux for 8 hr to prep. I.
~0 Citings
430. ORD and CD studies of saturated glycerides

By Gronowitz, Salo; Herslof, Bengt; Ohlson, Ragnar; Toregard, Bengt
DOI:10.1016/0009-3084(75)90058-4
The ORD and CD of optically active triglycerides as well as mono- and diglycerides were discussed. Sn-
ROCH2CH(OR1)CH2OR2 (I, R = R1 = Ac, R2 = acyl) and I (R = R1 = acyl, R2 = Ac) exhibited a neg. Cotton effect for
the n→Π* ester transition at 215-20 nm for the (S) configuration compds. (longer acyloxy group at C-1 than at C-3). The
ORD and CD curves at ∼200 nm were discussed. I (R2 = acyl, R = R1 = H) were converted to the 1-acyl-2,3-di(acyl)'-sn-
and 1,2-diacyl-3-(acyl)'-sn-glycerols via 1,2-dimesyl-3-acyl-sn-glycerols.
~1 Citing
431. Method for gentle lysis of Streptococcus sanguis and Streptococcus mutans
By Eisenberg, R. J.; Lillmars, K.
CAPLUS, DOI:10.1016/S0006-291X(75)80104-5
Methods were developed to gently lyse strains of S. Sanguis S. mutans. For S. sanguis, the procedure involved (a)
acetylation of the cells, (b) exposure of the cells to high concns. of lysozyme in the presence of a phosphate-sucrose
buffer and (c) lysis of the cells with Sarkossyl. For S. mutans glycerol was used as a stabilizer instead of sucrose and
dextranase was added along with lysozyme. Data were presented to indicate that 5 strains of each species were lysed
by >60%. By using the lysing procedure developed for S. mutas, the plasmid of S. mutans LM7 was identified by dye-
CsCl and sucrose d. centrifugation.
~0 Citings
432. Mass spectrometry identification of monoglycosyl glycerols

By Batrakov, S. G.; Il'ina, E. F.; Rozynov, B. V.; Sadovskaya, V. L.; Bergel'son, L. D.
From Bioorganicheskaya Khimiya (1975), 1(6), 725-36. Language: Russian, Database: CAPLUS
The mass spectra of trimethylsilyl and Ac derivs. of 3-O-α- and 3-O-β-D-glucopyranosyl-, 3-O-α- and 3-O-β-D-
galactopyranosyl-, and 3-O-α-D-mannopyranosyl-L-glycerols were obtained. The presence of monohexosyl glycerols in
the products of lipid deacylation (as acetates or trimethylsilyl esters) could be reliably detd. by using combined gas
chromatog.-mass spectrometry. A method for identifying monoglycosyl diglycerides in lipid exts. was developed. A mixt.
of H2O-sol. products of alk. deacylation of bulk lipids was acetylated with Ac2O in pyridine, and the residue, after evapg.
the acetylation reagents, was sepd. from the P-contg. compds. by filtration through Al2O3 and analyzed by gas
chromatog.-mass spectrometry. In the presence of the compds., the mass spectra of which were characteristic of
hexaacetates of monoglycosyl glycerols, the mixt. was deacetylated in alkali, then deuteroacetylated, and analyzed by
the combined method to det. the cyclic form of glycosyl glycerol. To det. the character of the carbohydrate residue, the
mixt. of deuterated acetates of trimethylsilyl esters was treated by acid methanolysis, and the products were identified by
the given method as trimethylsilyl esters.
~2 Citings
433. Esters of monoglycerides and diacetyltartaric acid

By Minaeva, S. V.; Lekhter, A. E.; Belova, S. M.; Marshanova, Z. T.; Shmidt, A. A.
From Maslozhirovaya Promyshlennost (1975), (1), 16-17. Language: Russian, Database: CAPLUS
Excess Ac2O converted tartaric acid to diacetyltartaric anhydride, which esterified n-C17H35CO2CH2CH(OH)CH2OH at
90° to give mixts. contg. ≤64% n-C17H35CO2CH2CH(OH)CH2O2C[CH(OAc)]2CO2H.
~0 Citings
434. Diol inositol phosphatides in polar lipids of Helianthus annuus

By Stefanov, K.; Popov, A.
From Doklady Bolgarskoi Akademii Nauk (1975), 28(10), 1391-4. Language: English, Database: CAPLUS
Ground sunflower samples extd. with CHCl3-MeOH (2:1), dialyzed thru a rubber membrane, and chromatographed on a
kieselguhr column (eluted with petroleum ether) yielded, in the inositol phosphatide fraction of the polar lipids, phosphoric
acid, inositol, glycerol, sugars, diols, and fatty acids (C14:0, C16:0, C16:1, C18:0, C18:1, and C18:2). CHCl3-MeOH-
25%NH3 (78:22:2) elution of sample from silica gel G and silica gel-kieselguhr showed the presence of 1-
phosphatidylinositol. The polyols of a 2nd fraction were acetylated and chromatographed to reveal the presence of
ethylene glycol, 1,2-butanediol, and traces of 1,3- and 2,3-butanediols.
~0 Citings
435. 1,4-Benzodiazepin-2-one derivative pharmaceuticals

By Kajfez, Franjo; Kovac, Tomislav; Sunjic, Vitomir
From Ger. Offen. (1975), DE 2264794 A1 19750123, Language: German, Database: CAPLUS
Twelve benzodiazepinones I [R = H, Me; R1 = OCH2CH2OH, 2,3-(isopropylidenedioxy)propoxy (II),
OCH2CH(OH)CH2OH (III), O2CCCl3; R2 = H, Cl], useful as anticonvulsants, muscle relaxants, and hypnotics, were
prepd. by treating I (R1 = Cl) with R1H or I (R1 = OH) with Cl3CCOCl. III could also be prepd. by hydrolysis of II. I (R1 =
Cl) were prepd. by chlorination of I (R1 = OH) with SOCl2. LD50 of I were 2500-6000 mg/kg orally. The anticonvulsant,
muscle relaxant and hypnotic effects were compared with those for diazepam, medazepam, and oxazepam.
~0 Citings
436. Use of Polynol A in the production of fine pastries

By Lucny, Miroslav; Kucirek, Miroslav
From Mlynsko-Pekarensky Prumysl a Technika Skladovani Obili (1976), 22(6), 184-7. Language: Czech, Database:
CAPLUS
The first part of a review with 27 refs. Monoacylglycerols, used as emulsifiers and antistaling additives in bakery
products are characterized and their effects on the quality of bakery products are discussed. Lactylated and acetylated
glycerol esters are discussed.
~0 Citings
437. Use of gas chromatography for the determination of water and glycerol in soap
By Monseigny, A.; Torre, M.; Vigneron, P. Y.
From Revue Francaise des Corps Gras (1976), 23(11), 599-604. Language: French, Database: CAPLUS
The water and glycerol [ 56-81-5 ] in toilet soaps were detd. with good precision even in the presence of additives. The
water was extd. with acetone and detd. on a column of Porapack Q with a thermal cond. detector. The glycerol was
sepd. by pptn. of fatty acids as Ba soaps, acetylated, and detd. on a column of Chromosorb CQ with a flame ionization
detector.
~0 Citings
438. The synthesis of chiral glycerides starting from D- and L-serine

By Lok, C. M.; Ward, J. P.; Van Dorp, D. A.
Edited By:Naudet, M.; Ucciani, E.; Uzzan, A
From Actes Congr. Mond. - Soc. Int. Etude Corps Gras, 13th (1976), Sect. E, 15-20. Language: English, Database:
CAPLUS
Chiral glycerides were prepd. starting from D- and L-serine by a multistep stereospecific sequence. E.g., L-serine was
converted by diazotization and esterification into Me L-glycerate, this by acetalization and redn. to 2,3-O-isopropylidene-
sn-glycerol, which was converted by sequential chlorination, hydrolysis, and cyclocondensation to D-glycidol (I). I could
be acylated, then esterified with a fatty acid to give a diglyceride mixt., which could be isomerized by heating to 100%
1,3-diglycerides, or its hydroxyl group could be protected by a trityl group and it could be converted into a 1,2-diglyceride.
Both types of diglycerides could be converted conventionally into sn-triglycerides.
~0 Citings
439. Synthesis and properties of sulfur-35-, carbon-14-, and tritium-labeled S-alkyl glycerol ethers and
derivatives
By Ferrell, William J.; Garces, Antonio; Desmyter, Etienne A.
DOI:10.1016/0009-3084(76)90022-0
Radioactive S-alkyl glycerol ethers (>99% pure) were synthesized with 35S, 14C and 3H labels as well as 3H/35S double
labels. The synthesized compds. were converted to various derivs. which can serve to characterize the S-alkyl glycerol
ethers. These included the isopropylidene deriv., oxidn. with periodate to the aldehyde followed by redn. with LiAlH4 to
the alc., and reaction of the alc. with Ac2O to form the acetate deriv. The gas liq. chromatog. behavior of the aldehyde
and acetate derivs. of both S-alkyl glycerol ethers and O-alkyl glycerol ethers on EGSS-X was compared.
~1 Citing
440. Surfactant
By Horikawa, Kazuo; Masuyama, Shinroku; Yasuhara, Toki; Imamura, Tamao
A fatty acid monoester of glycerol was esterfied with an acetylated amino acid to prep. hydrophilic, pleasant-smelling
surfactants useful in foods, cosmetics, etc. Thus, glycine [56-40-6] was treated with Ac2O [108-24-7] in water to prep. N-
acetylglycine [543-24-8] which was added to molten glycerol monopalmitate [26657-96-5] contg. AcONa to prep. a waxy
surfactant with acid value 21, OH value 158, and N content 3.3%.
~0 Citings

441. New synthesis of natural plasmalogens
By Evstigneeva, R. P.; Serebrennikova, G. A.; Vasilenko, I. A.
Edited By:Naudet, M.; Ucciani, E.; Uzzan, A
From Actes Congr. Mond. - Soc. Int. Etude Corps Gras, 13th (1976), Sect. E, 23-7. Language: English, Database:
CAPLUS
Plasmogen I (R = NH2) was prepd. from glycerol II, which was prepd. in 71-3% yield, by reaction with
Cl2P(O)OCH2CH2R1 (III; R1 = phthalimido), followed by hydrolysis. I (R = N+Me3Cl-) was prepd. by reaction of II with III
(R1 = Cl), followed by NMe3. The stability of glycerol alkenyl ethers under phthaloyl group removal conditions made this
a potential protective group for aldehydogenic phospholipid prepn.
~0 Citings
442. Mode of action of penicillins in vivo and in vitro in Bacillus megaterium

By Oka T
From Antimicrobial agents and chemotherapy (1976), 10(4), 579-91, Language: English, Database: MEDLINE
A new system in which the in vivo and in vitro formation of cross-links in the peptidoglycan of Bacillus megaterium can
be compared directly has been developed. The method for the determination of the in vivo cross-linking consists of
lysozyme digestion of acetylated [(14)C]diaminopimelic acid-labeled cells and Bio-Gel P-6 gel filtration of the digest.
The elution profile indicates the cell wall synthesized in vivo consists of highly cross-linked fractions (44%),
bisdisaccharide peptide(s) (38%), and disaccharide peptide(s) (18%). The in vitro system showed a high synthetic
activity of cross-linked peptidoglycan. The synthesis was inhibited completely by 83.3 mug of ristocetin or vancomycin
per ml or 10(-4) M p-chloromercuribenzoate and inhibited only partially by penicillins. The polymerization was
stimulated by high concentrations of sucrose, glycerol, amino acids, or dimethyl sulfoxide. The formation of cross-links
was inhibited 50% at 0.3 mug of dicloxacillin per ml and 90% at 0.5 mug or more. It was also stimulated by high
concentrations of sucrose, glycerol, or dimethyl sulfoxide. Effective concentrations of dicloxacillin on the growth,
viability, and morphology of B. megaterium were determined. Sharp inhibition of cross-linking occurred in vivo and in
vitro at these effective concentrations, whereas the incorporation of [(14)C]-diaminopimelate into bacterial cells was not
affected at all. Cell-bound dicloxacillin reduced severely the degree of cross-linking in the cell wall synthesized after
transfer to a dicloxacillin-free medium. Cell wall synthesized in the presence of dicloxacillin showed a higher rate of
turnover than did the normal cell wall. Moreover, disaccharide peptide(s) was degraded faster than was
bisdisaccharide peptide(s) in dicloxacillin-treated cells. From these observations, the primary target of penicillin action
in B. megaterium is discussed in relation to the inhibition of cross-linking, penicillin-binding components, and cell lysis.
~12 Citings

443. Mode of action of penicillins in vivo and in vitro in Bacillus megaterium
By Oka, Tetsuo
From Antimicrobial Agents and Chemotherapy (1976), 10(4), 579-91. Language: English, Database: CAPLUS,
DOI:10.1128/AAC.10.4.579
A new system in which the in vivo and in vitro formation of crosslinks in the peptidoglycan of B. megaterium can be
compared directly was developed. The method for the detn. of the in vivo crosslinking consists of lysozyme digestion of
acetylated 14C-diaminopimelic acid-labeled cells and Bio-Gel P-6 gel filtration of the digest. The elution profile indicated
the cell wall synthesized in vivo consisted of highly crosslinked fractions (44%), bisdisaccharide peptide(s) (38%), and
disaccharide peptide(s) (18%). The in vitro system showed a high synthetic activity of crosslinked peptidoglycan. The
synthesis was inhibited completely by 83.3 µg of ristocetin [1404-55-3] or vancomycin [1404-90-6]/ml or 10-4M p-
chloromercuribenzoate and inhibited only partially by penicillin [1406-05-9] derivs. The polymn. was stimulated by high
concns. of sucrose, glycerol, amino acids, or dimethyl sulfoxide. The formation of crosslinks was inhibited 50% at 0.3 µg
of dicloxacillin [3116-76-5]/ml and 90% at ≥0.5 µg. It was also stimulated by high concns. of sucrose, glycerol, or
dimethyl sulfoxide. Effective concns. of dicloxacillin on the growth, viability, and morphol. of B. megaterium were detd.
Sharp inhibition of crosslinking occurred in vivo and in vitro at these effective concns., whereas the incorporation of 14C-
diaminopimelate into bacterial cells was not affected at all. Cell-bound dicloxacillin decreased severely the degree of
crosslinking in the cell wall synthesized after transfer to a dicloxacillin-free medium. Cell wall synthesized in the
presence of dicloxacillin showed a higher rate of turnover than did the normal cell wall. Moreover, disaccharide
peptide(s) was degraded faster than was bisdisaccharide peptide(s) in dicloxacillin-treated cells. The primary target of
penicillin action in B. megaterium is discussed in relation to the inhibition of crosslinking, penicillin-binding components,
and cell lysis.
~1 Citing
444. Isolation of glyceryl esters of caffeic and p-coumaric acids from pineapple stems
By Takata, Ronald H.; Scheuer, Paul J.
From Lloydia (1976), 39(6), 409-11. Language: English, Database: CAPLUS
The antioxidant glyceryl esters I R = H, R1 = OH, H) were isolated from pineapple stems and their structures detd. by
spectral anal. and conversion to their acetates (R = Ac).
~7 Citings
445. Heterocycles from carbohydrate precursors. Part II. L-threo-2,3-Hexodiulosono-1,4-lactone as a precursor

for other heterocyclic compounds
By El Ashry, El S. H.
6215(00)85947-9
Treatment of I and II with H2NNHMe gave the unexpected, rearranged heterocycles III and IV, resp. Their structures
were confirmed by IR, NMR, and mass spectral data. In contrast, treatment of I and II with H2NNHPh or H2NNHBz gave
the expected 2,3-dihydrazone derivs.
~2 Citings
446. Glycerol based additives - additive synthesis

By Sehovic, Djurda; Jovanovic, Karmela
From Prehrambeno-Tehnoloska Revija (1976), 14(3-4), 2-4. Language: Croatian, Database: CAPLUS
By direct transesterification in a stream of inert gas, the corresponding monoglycerides were obtained from glycerol and
hydrogenated and refined coconut, palm and sunflower oils. The yield was 37-49% (after recrystn.). Esterification in
inert solvent, gave products with 70-90% monoglyceride content. The acetylation products of monoglycerides obtained
with Ac2O or AcCl, were identified by IR spectrometry and thin-layer chromatog.
~0 Citings
447. Effect of chemical modifications on the ultrastructure of corn, waxy maize, and tapioca starches
By Chabot, J. F.; Hood, L. F.; Allen, J. E.
From Cereal Chemistry (1976), 53(1), 85-91. Language: English, Database: CAPLUS
Unmodified and modified tapioca, corn, and waxy maize starch [9005-25-8] were examd. by light and electron (scanning
and transmission) microscopy. Modified starches investigated included those cross-linked with POCl3 or
epichlorohydrin, and (or) derivatized with propylene oxide or Ac2O. Only slight differences were noted in the structure of
granules cross-linked with different reagents. Some samples of uncooked modified starches showed granule breakage
and partial gelatinization. Gelatinized prepns. of unmodified tapioca consisted of few granules and a mass of
interconnected fibrils of variable dimension. Hydroxypropyl distarch phosphate [53124-00-8] and acetylated distarch
glycerol [53123-84-5] from tapioca had intact granules contg. a diffuse material as well as intergranular fibrils.
Unmodified waxy maize and all modified waxy maize starches had little or no extragranular fibrillar material. Unmodified
and modified corn starch had small granules embedded in a fine fibrillar matrix. Some of the modified granules also had
diffuse fibrillar material in the central cavity of the granule. Chem. modification of corn and tapioca starch caused a redn.
in the amt. of extragranular starch, with the maintenance during cooking of an intact envelope around a fibrillar filled
cavity.
~4 Citings
448. Characterization of D(-)-glyceric acid in a glycolipid from Nocardia caviae

By Pommier, Marie T.; Michel, Georges
From Biochimica et Biophysica Acta, Lipids and Lipid Metabolism (1976), 441(2), 327-33. Language: French,
Database: CAPLUS
A glycolipid was found in a strain of N. caviae. It consists of glucose, myristic, palmitic, and stearic acids, and a
polyhydroxylated acid. The structure of this hydroxyacid was demonstrated by the identification of the product glycerol
after LiAlH4 redn. of the glycolipid Me ester and subsequent hydrolysis, by comparison of the ir spectra of the
hydroxyacid and glyceric acid, by gas chromatog. of acetylated Me and Et esters of the polyhydroxylated acid and of std.
glyceric acid and by mass spectrometry of the diacetylated Me ester. The hydroxyacid from the glycolipid is D(-)glyceric
acid, a compd. rarely found among natural products.
~0 Citings
449. Characterisation of D(-)glyceric acid from Nocardia caviae (author's transl)

By Pommier M T; Michel G
From Biochimica et biophysica acta (1976), 441(2), 327-33, Language: French, Database: MEDLINE
A glycolipid was found in a strain of Nocardia caviae. It consists of glucose, myristic, palmitic and stearic acids and a
polyhydroxylated acid. The structure of this hydroxyacid was demonstrated by the identification of the product glycerol
after LiA1H4 reduction of the glycolipid methyl ester and subsequent hydrolysis, by comparison of the infrared spectra
of the hydroxyacid and glyceric acid, by gas chromatography of acetylated methyl and ethyl esters of the
polyhydroxylated acid and of standard glyceric acid and by mass spectrometry of the diacetylated methyl ester. The
hydroxyacid from the glycolipid is D(-)glyceric acid, a compound rarely found amongst natural products.
~0 Citings
450. Cell wall of Actinomyces rimosus LST-118

By Dmitrieva, N. F.; Naumova, I. B.; Streshinskaya, G. M.; Panina, L. I.
From Bioorganicheskaya Khimiya (1976), 2(6), 815-21. Language: Russian, Database: CAPLUS
Teichoic acid was sepd. from the nucleic acid, peptidoglycan (murein), and polyphosphate components of A. rimosus cell
walls, and its structure was detd. by acid, alk., and phosphomonoesterase hydrolysis. Based on the products of
hydrolysis and the ratio of total phosphate to terminal monophosphate groups, each mol. of teichoic acid consists of an
av. of 10 glycerophosphate groups, with the glycerol units joined by 1,3-phosphate diester bonds. No sugars were obsd.
attached to the teichoic acid, but each mol. of this polymer contained an av. of 3 Ac groups. The total cell wall ext.
contained 2.3% (by wt.) Ac groups which yields a 4:1 Ac/teichoic acid ratio. The crude cell wall prepn. contained
muramic acid, glucosamine, and galactosamine in a 1:1.98:0.58 molar ratio. Based on this molar ratio, the assumption
that these sugars are acetylated, and the no. of Ac groups not bound to teichoic acid, the amts. of muramic acid,
glucosamine, and galactosamine in the A. rimosus cell wall are 43.53, 86.19, and 25.25 µmoles/100 mg cell wall. Thus,
for each 20 muramic acid residues in the cell wall, there is 1 teichoic acid mol. contg. 10 glycerophosphate units.
~0 Citings
451. Antiallergic pharmaceutical preparations

By Gorvin, John H.
5-Acetylsalicylic acid (I) [13110-96-8] and its salts, esters, and amides inhibit reagin-mediated allergy free actions such
as asthma, allergic rhinitis, conjunctivitis, urticaria, and eczema by inhibiting the release of anaphylactic mediators. For
example, a sirup was prepd. contg. I Na salt 5.0, sucrose 60.0, Me hydroxybenzoate 0.1, glycerin 10.0 g, flavoring, and
water to 100.0 ml.
~0 Citings
452. Alkoxy-substituted thiophenecarboxylic acid compounds

By Parker, Roger Alan
5-Alkoxy-2-thiophenecarboxylic acids (I; R = H, Me, Et, CH2CHCH2, Na; R1 = dodecyl, tetradecyl, hexadecyl, octadecyl,
3,7,11,15-tetramethylhexadecyl), useful as hypolipemics, are prepd. by std. procedures. Thus, reaction of
Me(CH2)13OH with 5-chloro-2-thiophenecarboxylic acid in Me2C6H4 in presence of NaH gives after 64 h at reflux I (R =
H, R1 = tetradecyl) (II). Treatment of rats for 4 days with daily doses of 150 mg II/kg lowers cholesterol and triglycerides
by 54 and 83%, resp.
~0 Citings
453. Acetoxyglycerol acetal derivatives of mono- and polyformyloctadecanoate esters: plasticizers for
poly(vinyl chloride)
By Neff, W. E.; Frankel, E. N.; Pryde, E. H.; Riser, G. R.
From Journal of the American Oil Chemists' Society (1976), 53(4), 152-6. Language: English, Database: CAPLUS,
DOI:10.1007/BF02586355
Acetoxy mono-, di-, and triglycerol acetals from safflower oil and linseed oil methyl esters were good primary plasticizers
for PVC [9002-86-2] and showed less migration, better heat-stability, and higher tensile strength in formulations than the
conventionally used dioctyl phthalate plasticizer. Acetoxyglycerol acetals of hydroformylated Me and Bu oleate were
good secondary plasticizers. The Me and Bu (acetoxyglycerol acetal) esters were prepd. either by direct acetylation of
alkyl 9(10)-formyloctadecanoate with glycerol (I) [ 56-81-5 ] or by transacetylation of alkyl 9(10)-
dimethoxymethyloctadecanoate with I. In either method a mixt. of dioxolane and dioxane ring derivs. was formed.
Acetylation of the free OH groups in these derivs. gave the acetoxymethyldioxolanyl and acetoxydioxanyl plasticizers.
~6 Citings
454. 4-Oxopiperidine derivatives

By Brunetti, Heimo; Rody, Jean; Soma, Nobuo
4-Piperidinone cyclic ketals I (R = H, Me, H2C:CHCH2, PhCH2, O, Ac; R1 = e.g. H, Me, HOCH2, AcOCH2; n = 1, 2) and
II, useful as light stabilizers for polymers, are prepd. by treatment of 2,6-diethyl-2,3,6-trimethyl-4-piperidinone (III) with the
appropriate polyhydroxy compds. Thus, reaction of III with HO(CH2)2OH in PhMe in presence of 4-MeC6H4SO3H gives
after 12 h at reflux I (R = R1 = H), which when added to polypropylene (0.25 wt.%) increases irradn. tolerance by a factor
of 3.5.
~0 Citings
455. Uncommon results of glycosidase action: Part II. The conversion of 2,6-anhydro-1-deoxy-D-galacto-hept-1-
enitol into 1-deoxy-D-galacto-heptulose by β-D-galactosidase
By Brockhaus, Manfred; Lehmann, Jochen
6215(00)85451-8
The title heptenitol I was prepd. by benzylidenation and acetylation of II (R = CO2Me, R1 = H) followed by redn.,
tosylation, deketalation, acetylation, iodine exchange, dehydrohalogenation, and deacetylation. β-D-galactosidase
catalyzed the conversion of I into II (R, R1 = Me, OH) and in the presence of glycerol, II (R = HOCH2CHOHCH2O, R1 =
Me), a substrate from β-D-galactosidase, was also formed.
~28 Citings
456. Uncommon results of glycosidase action. Part IV. The stereochemistry of the addition of glycerol to D-
galactal, catalyzed by β-D-galactosidase
By Lehmann, Jochen; Zieger, Berit
6215(00)83405-9
Reaction of D-galactal-2-d with glycerol in the presence of β-D-galactosidase gave I. NMR showed that the H is
introduced onto C-2 in the trans position to the aglycone. 4-MeC6H4SO3H-catalyzed reaction of PhOH with peracetyl-D-
galactal-2-d gave II.
~8 Citings
457. Toilet soap cakes

By Schubert, Warren R.
The title product was produced by bonding soap chips with high-mol. wt. polyethylene glycol (I) [25322-68-3]. Thus, a
mixt. of soap chips [Na soap of coconut oil-tallow mixt. (17:83), H2O content ∼11.5%] 88.50, 50% aq. SnCl4 soln. 0.15, I
2.00, H2O 1.00, TiO2 0.60, hydrolyzed protein 3.00, Na fatty isothionate 2.00, glycerol 0.50, acetylated lanolin 1.00, and
perfume 1.25% was rolled at 34-7°, extruded, and cut to give a specimen with improved hardness, fracture resistance,
smoothness, and brightness.
~8 Citings
458. Synthesis of 1-O-alkenyl ethers of glycerol of natural structure

By Chebyshev, A. V.; Serebrennikova, G. A.; Evstigneeva, R. P.
RCH2CH(OEt)2 (I; R = n-C14H29) reacted with SOCl2 or PCl5 and then with HOAc to give RCH2CH(OAc)OEt, which
eliminated HOAc to give RCH:CHOEt and reacted with sn-glycerol 2,3-cyclocarbonate (II) to give 80.2% III. Treating I [R
= n-C14H29, Z-Me(CH2)7CH:CH(CH2)6] with II gave the sym. acetals, which were converted into IV with HOAc. IV were
deacetylated to give 87.5-92.5% V, then hydrolyzed to 90.2-2.1% sn-RCH:CHOCH2CH(OH)CH2OH.
~2 Citings
459. Substituted p-menthanes

By Watson, Hugh R.; Rowsell, David G.; Browning, John H. D.
The p-menthane-3-carboxylic acid esters I (R = CH2CH2OH, CH2CH2OCH2CH2OH, CHMeCHMeOH, 2,2-dimethyl-1,3-
dioxolan-4-ylmethyl, etc.) were prepd. by esterification of RH with p-menthane-3-carbonyl chloride.
~19 Citings
460. Substances to stimulate acetic acid fermentation. IV. Isolation and identification of the substance to
stimulate acetic acid production from sake cake
By Nanba, Tsuyoshi; Takeuchi, Tokuo
From Nippon Shokuhin Kogyo Gakkaishi (1977), 24(11), 576-81. Language: Japanese, Database: CAPLUS
The neutral fraction in sake cake sepd. on a multicolumn of Amberlite IR-120 (H+) and Amberlite IRA-410 (OH-) had a
superior effect for the stimulation of AcOH [64-19-7] fermn. The effective substance in this fraction was further purified
by column chromatog. of active C-Celite, Celite, and Sephadex G-15, and was isolated on a paper chromatogram with
several solvent systems. It had the same Rf as that of glycerol. It was acetylated and identified by gas chromatog. and
IR and NMR spectra. It markedly stimulated the prodn. of AcOH and also reduced the lag time in growth of acetic acid
bacteria strain No. 2.
~0 Citings
461. Studies on complex lipids. Synthesis of phosphatidylethanolamine and phosphatidylinositol by direct

acylation of glycerolphosphoric acid esters by aliphatic acid anhydrides
By Sukhanov, V. A.; Sergovskaya, N. L.; Shvets, V. I.; Evstigneeva, R. P.
From Zhurnal Obshchei Khimii (1977), 47(9), 2130-6. Language: Russian, Database: CAPLUS
Glyceride phosphates I was obtained in 58-89% yields in 3 steps from 1,2-di-O-benzylglycerol by phosphorylation with
(HO)2P(O)(OR), debenzylation, and esterification with palmitic acid. Similarly
HOCH2CH(OH)CH2OP(O)(OH)OCH2CH(NHCO2CH2Ph)CO2CH2Ph was obtained in 76.7% from 1-O-benzylglycerol by
acetylation, debenzylation, phosphorylation, sapon., and treatment with DL-serine.
~0 Citings
462. Rapid GLC determination of therapeutic plasma glycerin levels

By Goehl T J; Pitlick W H; Shiu G K; Pirakitikulr P
From Journal of pharmaceutical sciences (1977), 66(7), 1027-9, Language: English, Database: MEDLINE
A new rapid and inexpensive method for the determination of therapeutic plasma glycerin concentrations is described.
In this method, acetic anhydride and pyridine are added to 15 microliter of plasma. After brief incubation and
centrifugation, an aliquot of the supernate is injected directly onto the 3% OV-1 column. A linear calibration curve was
found in the 0.05--3-mg/ml range, with the precision of the assay estimated to be +/-5.5% (RSD). The method was
used to determining preliminary pharmacokinetic data in the rabbit.
~0 Citings
463. Qualitative TLC separation of acetoglycerides

By Neissner, R.
From Fette, Seifen, Anstrichmittel (1977), 79(1), 24-8. Language: German, Database: CAPLUS
Tech. acetylated glycerides were sepd. and identified by thin-layer chromatog. of a 1-3% soln. in CHCl3 on silica gel 60
plates using a 60:40:1 petroleum ether (b. 40-60°)-Et2O-HOAc mixt. as liq. phase, spraying with 0.1% alc. 2,7-
dichlorofluorescein, and detecting with UV light. Small amts. of acetylated glycerides were detected in hard fat and
identified as 3-aceto-1,2-dimyristin [62724-24-7] and 2-aceto-1,3-dimyristin [58546-05-7].
~0 Citings
464. Preparation and properties of α-monoglycerides of naphthenic acids

By Artamonov, A. F.; Bektursynov, B.; Goryaev, M. I.
From Izvestiya Akademii Nauk Kazakhskoi SSR, Seriya Khimicheskaya (1977), 27(5), 85-8. Language: Russian,
Database: CAPLUS
Glycerol 1-naphthenate and HOCH2CH(OH)CH2O2CR (R = cyclopentamethyl, cyclopentyl) were prepd. by acid
hydrolysis of the 2,3-isopropylidene deriv., which was prepd. by successive treatment of glycerol with Ac2O and the resp.
acid chloride.
~0 Citings
465. Nonmedicinal microbe-killing composition

By Inoue, Shigeo; Miyamoto, Norioki; Shimizu, Haruo
Antimicrobial compds. RXCH:CHCO2Y [R = C1-20 alkyl or C2-20 alkylene; X = S, SO or SO2; Y = H, alkali, alk. earth,
NH4, C1-20 alkyl, C2-20 alkylene, a radical obtained by OH removal from a polyhydric alc., acetylated glycerol, or an
(R1O)nR2 group where R1 = ethylene or propylene, n = integer 1-20, and R2 = H or C1-20 alkyl] were added as
preservatives in 1-25% amts. to non-pharmaceutical (e.g. cosmetic) compns. contg. org. substances which are decompd.
or damaged by microorganisms. For example, Me β-n-butylsulfinylacrylate (I) [62739-65-5] inhibited growth of
Escherichia coli, Proteus vulgaris and Pseudomonas aeruginosa at min. concns. of 50, 50 and 500 ppm, resp., and also
showed good inhibition of common mold and yeast species. A hairdressing was prepd. from liq. paraffin 10, petrolatum
3, beeswax 5, lanolin 2, and polyoxyethylene sorbitol monostearate 3% with small amts. of coloring and perfume and 0.2
or 0.5% I all dild. with H2O to 100%. The I inhibited microbial growth for ≤30 days, and showed good compatibility with
the emulsion.
~0 Citings
466. Myxospore coat synthesis in Myxococcus xanthus: in vivo incorporation of acetate and glycine
By Filer D; White D; Kindler S H; Rosenberg E
From Journal of bacteriology (1977), 131(3), 751-8, Language: English, Database: MEDLINE
Myxospore coat synthesis in Myxococcus xanthus was studied by incorporation of [(14)C]acetate into intermediates in
the biosynthesis of coat polysaccharide and into acid-insoluble material during vegetative growth and after glycerol
induction of myxospores. During short labeling periods at 27 degrees C, the radioactivity was shown to be located
primarily in N-acetyl groups rather than sugar moieties. Two hours after glycerol induction, the pools of N-
acetylglucosamine 6-phosphate and uridine 5'-diphosphate-N-acetylgalactosamine (UDPGalNAc) plus uridine 5'-
diphosphate-N-glucosamine increased about twofold and were labeled at twice the rate measured for vegetative cells.
The increased rate of synthesis of UDPGalNAc and its precursors could be correlated with increased enzyme activities
measured in vitro. Controlled acid hydrolysis revealed that the galactosamine portion of the myxospore coat was N-
acetylated. After glycerol induction, the incorporation of acetate into acid-insoluble material increased threefold. This
enhanced incorporation was sensitive to neither penicillin nor d-cycloserine. In contrast, bacitracin inhibited the
incorporation of [(14)C]acetate into acid-insoluble material more effectively 2 h after myxospore induction than during
vegetative growth. Chloramphenicol added to cells 90 min after induction blocked further increase in the rate of
[(14)C]acetate incorporation. Since the myxospore coat contains glycine, polymer synthesis was also measured by
chloramphenicol-insensitive [(14)C]glycine incorporation into acid-insoluble material. Although protein synthesis
decreased after glycerol induction, glycine incorporation increased. Two hours after induction, glycine incorporation
was only 75% inhibited by chloramphenicol and rifampin. The chloramphenicol-insensitive rate of incorporation of
[(14)C]glycine increased during the first hour after myxospore induction and reached a peak rate after 2 to 3 h. The
chloramphenicol-resistant incorporation of [(14)C]glycine was resistant to penicillin but sensitive to bacitracin.
~6 Citings
467. Myxospore coat synthesis in Myxococcus xanthus: in vivo incorporation of acetate and glycine
By Filer, D.; White, David; Kindler, S. H.; Rosenberg, E.
From Journal of Bacteriology (1977), 131(3), 751-8. Language: English, Database: CAPLUS
Myxospore coat synthesis in M. xanthus was studied by incorporation of acetate-14C into intermediates in the
biosynthesis of coat polysaccharide and into acid-insol. material during vegetative growth and after glycerol induction of
myxospores. During short labeling periods at 27°, the radioactivity was located primarily in N-acetyl groups rather than
sugar moieties. Two h after glycerol induction, the pools of N-acetylglucosamine 6-phosphate and UDP-N-
acetylgalactosamine (UDPGalNAc) plus UDP-diphosphate-N-glucosamine increased ∼2-fold and were labeled at twice
the rate measured for vegetative cells. The increased rate of synthesis of UDPGalNAc and its precursors could be
correlated with increased enzyme activities measured in vitro. The galactosamine portion of the myxospore coat was N-
acetylated. After glycerol induction, the incorporation of acetate into acid-insol. material increased 3-fold. This enhanced
incorporation was not sensitive to penicillin or D-cycloserine. Bacitracin inhibited incorporation of acetate into acid-insol.
material more effectively 2 h after myxospore induction than during vegetative growth. Chloramphenicol added to cells
90 min after induction blocked further increase in the rate of acetate incorporation. Although protein synthesis decreased
after glycerol induction, glycine incorporation increased. Two h after induction, glycine incorporation was only 75%
inhibited by chloramphenicol and rifampin. The chloramphenicol-insensitive rate of incorporation of glycine increased
during the first h after myxospore induction and reached a peak rate after 2-3 h. The chloramphenicol-resistant
incorporation of glycine was resistant to penicillin but sensitive to bacitracin.
~7 Citings
468. Mixed esterified polyols

By Baudet, Pierre; Ricard, Jean Paul; Schulthess, Adrian
Six esters of inositol, ethylene glycol, glycerol, or propanediol were prepd. in several ways via conventional reactions.
Thus, 1,3-benzylideneglycerol was acetylated with 2-AcOC6H4COCl, hydrogenolyzed, and treated with 4-
ClC6H4OCMe2COCl to give (4-ClC6H4OCMe2CO2CH2)2CHO2CC6H4OAc-2. The products lowered cholesterol and
triglycerides in blood.
~1 Citing
469. Long-chain stereomeric 2-alkyl-4-methoxycarbonyl-1,3-dioxolanes in glycerol acetal synthesis

By Wedmid, Yuri; Baumann, Wolfgang J.
From Journal of Organic Chemistry (1977), 42(22), 3624-6. Language: English, Database: CAPLUS,
DOI:10.1021/jo00442a040
Acid-catalyzed condensation of a long-chain aldehyde (e.g., hexadecanal, cis-9-octadecenal) with Me glycerate quant.
produced cis- and trans-2-alkyl-4-methoxycarbonyl-1,3-dioxolanes. These stereomeric glycerate cyclic acetals are
separable by adsorption chromatog., owing to their significantly different polarities dependent upon the orienation of the
methoxycarbonyl function relative to the ring system. Configurational assignments are based on 1H and 13C NMR data.
Availability of configurationally pure, long-chain glycerate acetal opens a convenient route for the synthesis of the resp.
cis and trans 5-membered ring acetals of glycerol by redn. of the methoxycarbonyl function.
~2 Citings
470. Isolation and characterization of structural components of Bacillus cereus AHU 1356 cell walls
By Amano, Kenichi; Hazama, Setsuro; Araki, Yoshio; Ito, Eiji
From European Journal of Biochemistry (1977), 75(2), 513-22. Language: English, Database: CAPLUS,
DOI:10.1111/j.1432-1033.1977.tb11552.x
From lysozyme digests of N-acetylated cell walls of B. cereus, a polysaccharide fraction and a teichoic acid fraction were
isolated by ion-exchange and gel chromatog. The former fraction, accounting for 50% of the walls, contained N-
acetylglucosamine, N-acetylmannosamine, N-acetylgalactosamine, and glucose in a molar ratio of 4:1:1:1 together with a
small amt. of the peptidoglycan constituents. The latter fraction accounted for 5% of the walls and was composed of N-
acetylglucosamine, galactose, glycerol, and P in a molar ratio of 1:1.4:1:1 and a small amt. of the peptidoglycan
constituents. The mol. wt. of the polysaccharide fraction was ∼33,000. A stoichiometric amt. of muramic acid 6-
phosphate was detected in the polysaccharide fraction, which was probably involved in the linkage between
polysaccharide and peptidoglycan moieties. The polysaccharide moiety had an approx. mol. wt. of 28,000. A tentative
formulation of the most likely structure of the repeating unit is given.
~6 Citings
471. High-temperature gas chromatography of polyglycerol

By Itsikson, L. B.; Shul'gaitser, L. A.; Bulatnikov, V. V.
From Zhurnal Analiticheskoi Khimii (1977), 32(3), 630-2. Language: Russian, Database: CAPLUS
The structure of polyglycerol (I) [25618-55-7] was detd. by a programmed temp. gas chromatog. method similar to that
described by the author (1971) for the distribution of trimethylolpropane C3-12 fatty acid esters and includes the use of
columns with a small diam. with a low concn. of high-temp. liq. phase and a high linear rate of the carrier gas. OV-17
and PFMS-4 liq. phases were used, and I was acetylated with 1:1 Ac2O-pyridine. The gas chromatog. sepn. was carried
out by using a differential flame ionization detector and columns with a 5% liq. phase on Chromation N-GMDS. The
programmed temp. range was 100-310 (or 330°) and the carrier gas flow rate for He, H and air was 60, 40, and 300
ml/min, resp. The temp. of the detector and the vaporizer was 370 and 330°, resp. The retention indexes of glycerol
oligomers decrease with temp. and can be represented as a homologous series.
~0 Citings
472. Heterocycles from carbohydrate precursors. Part IV. Synthesis of some pyrazole derivatives having L-
threo and D-erythro side chains
By El Ashry, El Sayed H.; El Kilany, Yeldez; Singab, Farrag
6215(00)84240-8
Rearrangement of I (X = PhNHN; X1 = 4-R2-C6H4NHN; R = OH; R1 = H; R2 = Me, Cl, Br, iodo) gave the pyrazoles II
(R3 = Me, Cl, Br, iodo; R4 = R6 = H, R5 = OH). Periodate oxidn. of II (R3 = Me, R4 = R6 = H, R5 = OH) gave III (R7 =
Me, X2 = O). Similarly, rearrangement of the bis(hydrazones) I (X = X1 = 4-R2C6H4NHN, R = H, R1 = OH, R2 = Cl, Br,
iodo) gave the pyrazoles II (R3 = R4 = Cl, Br, iodo, R5 = H, R6 = OH). Periodate oxidn. of II (R3 = R4 = R5 = H, R6 =
OH) followed by condensation with R8CONHNH2 (R8 = H, Me, Cl, MeO, 4-pyridyl) gave III (R7 = H, X2 = R8CONHN).
~6 Citings
473. Determination of phosphorus:glycerol:acyl ratios in phospholipids

By Stearns, E. M., Jr.; Morton, W. T.
From Microchemical Journal (1977), 22(3), 283-7. Language: English, Database: CAPLUS, DOI:10.1016/0026-
265X(77)90023-6
Phospholipids (1-5 mg) are mixed with Me heptadecanoate as an internal std. One part of the sample is reduced with
Vitride in THF in a sealed tube for 50° for 1 h. The reaction products are acetylated in the same tube by treatment with
HOAc-Ac2O at 140°. After 1 h, total O-acyl and after 16 addnl. h, glycerol are detd. as the fully acetylated compds. by
gas chromatog. Another part of the sample is subjected to acidic hydrolysis, and total O-acyl and N-acyl groups are
detd. by gas chromatog. as fatty-acid Me esters. The aq. phase is heated to 100° with 6N HCl for 72 h, and P is
measured colorimetrically.
~0 Citings
474. Dermatological compositions containing an acylamino-carboxylic acid or an alkyl ester thereof

By Eberhardt, Hans; Brickl, Rolf Stefan
Skin-care products contain acylaminocarboxylic acids or their alkyl esters. The dermatol. products inhibit sebaceous
gland excretion and combat inflammation of the skin. N-acetylglycine octadecyl ester [52558-40-4] was prepd. from a
molten unit of glycine Et ester-HCl [623-33-6] and octadecanol [112-92-5] treated with gaseous HCl for 3 h; the base
[62546-11-6] was liberated from the solid glycine octadecyl ester-HCl [59404-67-0] obtained, and then acetylated. A
cream was formulated from N-acetylglycine hexadecyl ester [52558-56-2] 3.0, benzalkonium chloride 0.1, Cremophor O
4.0, glycerine monostearate 4.0, Lanette O 5.0, spermaceti 3.0, Cetiol V 10.0, and distd. H2O up to 100 parts. N-
Acetylglycine hexadecyl ester inhibited dinitrochlorobenzene-induced eczema in guinea pigs (46% more than in controls)
and inhibited sebacous gland excretion in human subjects.
~20 Citings
475. Dermatological compositions comprising acylaminocarboxylic acid derivatives

By Eberhardt, Hans; Brickl, Rolf S.
From Can. Pat. Appl. (1977), CA 1022849 A1 19771220, Language: English, Database: CAPLUS
Acrylaminocarboxylates R1CONR2CHR3(CH2)nCO2R4 are prepd. for topical formulation for therapeutic and cosmetic
purposes. Some of the activities of the compds. are sebaceous inhibition, antiinflammatory, antidandruff, and skin
conditioning. E.g., N-acetylglycine octadecyl ester [52558-40-4] was prepd. by transesterification of H2NCh2CO2Et.HCl
with octadanol and N-acetylation of the resulting glycine octadecyl ester-HCl [59404-67-0]. A cream was prepd. contg.
the following: N-acetylglcyine hexadecyl ester [52558-56-2] 3.0, benzalkonium chloride 0.1, ethoxylated satd. fatty alc.
4.0, glycerol monostearate 4.0, cetylstearyl alc. 5.0 cetaceum 3.0, decyl oleate 10.0 g and water to 100 mL.
~6 Citings
476. Antihypertonic preparation containing arylalanine derivatives

By Stone, Clement Addison
Pharmaceutical prepns. with increased antihypertonic activity comprise a decarboxylase inhibitor (I: R, R1, R2 and R3 =
H or C1-4 alkyl) or its salts and an arylalanine deriv. such as II where R, R1, R3 and R4 = H or C1-4 alkyl; and R2 = H,
halogen, HO, or C1-4 alkyl or an arylalanine deriv. such as III where R, R1, and R2 = H or C1-4 alkyl, X = O or NR3 with
R3 = H or C1-4 alkyl, and Z = O or OR4 with R4 = H or C1-4 alkyl and/or salts of these derivs. Prepn. of the arylalanine
derivs. is described. For example, DL-methyl-N-acetyl-3-(3-nitro-4-acetamidophenyl)-2-methylalanate [53526-34-4] was
treated with HCl, the product was hydrogenated over Pd/charcoal and filtered, and COCl2 was passed through the filtrate
to give DL-3-(benzimidazol-2-on-5-yl)-2-methylalanine-HCl (IV) [64563-05-9]. A suspension was prepd. from IV 10,
carbidopa [28860-95-9] 500, Veegum H.V. 300, methylparaben 50, kaolin 50 and glycerol 500 g in H2O to give 1 L. A
1.25 mg/kg dose of IV-carbidopa mixt. [64738-58-5] showed antihypertonic activity in rats, although IV was only active at
20 mg/kg and carbidopa was inactive at 25 mg/kg.
~0 Citings
477. Androst-5-en-17-one derivatives and their use in the preparation of pharmacologically active steroids
By Eder, Ulrich; Sauer, Gerhard; Haffer, Gregor; Neef, Guenter; Wiechert, Rudolf; Weber, Alfred; Popper, Alfred;
Kennecke, Mario; Mueller, Rudolf
A no. of 3-substituted 5-androsten-17-one derivs. were prepd. form the analogs substituted at the 17-position with
various hydrocarbon groups by fermn. with Mycobacterium. Thus, 3β-ethoxy-5-androsten-17-one (I) [62502-29-8] was
prepd. from 3β-ethoxy-5-etholestene (II) [986-19-6]. These 3-substituted 5-androsten-17-one compds. were furgher
modified chem. by redn. of the keto group or alkylating at the 17 position with organometallics to produce compds. such
as testosterone (III) [58-22-0], and by reacting with alkali metal acetylides, dehydrating, and reacting with Hg salts to form
5-pregnen-20-one compds. such as pregnenolone (IV) [145-13-1].
~2 Citings
478. Acetylated glycerols as dietary constituents: studies on their nutritional adaptation by rats
By Shapira J; Vann L S; Furst A
From Proceedings of the Western Pharmacology Society (1977), 20217-20, Language: English, Database: MEDLINE
~0 Citings
479. Acetylated glycerols as dietary constituents: studies on their nutritional adaptation by rats
By Shapira, J.; Vann, L. S.; Furst, A.
From Proceedings of the Western Pharmacology Society (1977), 20, 217-20. Language: English, Database: CAPLUS
Percent changes in wt. gain of rats given starch (>1%) or starch (31%) with glycerol [ 56-81-5 ] (40), monoacetin [26446-
35-5] (40), diacetin [25395-31-7] (40), or triacetin [102-76-1] (40%) in their feed were -75, -63, -27, 0, and +30 when the
growth differences in weeks 3-4 vs. weeks 12-13 and weeks 12-13 vs. weeks 25-6 (rat age) were compared. Total
growth on the acetin-contg. feeds was lower than that on the starch and starch-glycerol feeds in all growth periods,
although higher adaptation to the acetin-contg. feeds was shown.
~0 Citings
480. 2-[2-(4-Chlorophenoxy)-2-methylpropionyloxy]alkyl O-acetylsalicylates

From Fr. Demande (1977), FR 2337552 A1 19770805, Language: French, Database: CAPLUS
Esters I (Z = direct bond, alkylene, acyloxyalkylene; R and R1 are H, alkyl, hydroxyalkyl, or acyloxyalkyl or R and R1 are
part of a ring of ≤6 C atoms) were prepd. by O-acylation; I are useful as blood platelet aggregation inhibitors (no data)
and anticholesteremics. Thus, 1,3-benzylideneglycerol was treated with 2-AcOC6H4COCl, subjected to hydrogenolysis,
and O-acylated by 4-ClC6H4OCMe2COCl to give II which exhibited anticholesteremic activity.
~1 Citing
481. The scope of the reaction of hydrazines and hydrazones. Part VIII. Reactions of L-ascorbic and isoascorbic
acids with hydrazines related to sulfanilamide drugs
By Soliman, Raafat; El Ashry, El Sayed H.; El Kholy, Ibrahim E.; El Kilany, Yeldez
6215(00)83740-4
Various compds. related to the antibacterial sulfanilamide drugs were prepd. from dehydro-L-ascorbic acid or its D-
erythro analog by reaction with hydrazines related to sulfanilamide, sulfadiazine, sulfamerazine, sulfamethazine, and
sulfamethoxydiazine, whereby the 2-mono- and 2,3-bis-(hydrazones) were isolated. After opening of the lactone ring in
the bis(hydrazones) with alkali, nucleophilic attack on the carbonyl group of the imino nitrogen atom of the 3-hydrazone
residue gave 3-(L-threo-glycerol-1-yl)-1-phenyl- and -1-(p-sulfamylphenyl)-4,5-pyrazoledione 4-(p-
sulfamylphenylhydrazone) and the related 3-(D-erythro-glycerol-1-yl) compds. Whereas acetylation of L-threo-2,3-
hexodiulosono-1,4-lactone 2,3-bis(p-sulfamylphenylhydrazone) (I) and 3-(L-threo-glycerol-1-yl)-1-(p-sulfamylphenyl)-4,5-
pyrazoledione 4-(p-sulfamylphenylhydrazone) (II) gave the O-acetyl derivs., benzoylation of II gave the di-N-benzoyltri-O-
benzoyl compd. Reaction of I with CuCl2 gave 3,6-anhydro-3-(p-sulfamylphenylazo)-L-xylo-2-hexulosono-1,4-lactone 2-
(p-sulfamylphenylhydrazone). The 3-(L-threo-glycerol-1-yl)-1-(p-sulfamylphenyl)flavazole (III) was prepd. by the
rearrangement of 3-[(1-p-sulfamylphenyl)hydrazono-L-threo-trihydroxybutyl]-2-quinoxalinone (IV). Periodate oxidn. of II-
IV gave 3-formyl-1-(p-sulfamylphenyl)-4,5-pyrazoledione 4-(p-sulfamylphenylhydrazone), 3-{1-[(p-
sulfamylphenyl)hydrazono]glyoxal-1-yl}-2-quinoxalinone, and 3-formyl-1-(p-sulfamylphenyl)flavazole, resp. The IR and
NMR spectral data for some of these derivs. are reported.
~3 Citings
482. Synthesis of some 2,3-dihydroxypropyl derivatives of purine bases

By Holy, Antonin
From Collection of Czechoslovak Chemical Communications (1978), 43(11), 3103-17. Language: English, Database:
CAPLUS, DOI:10.1135/cccc19783103
From adenine, 2,6-diaminopurine, 2-methylthioadenine, and 2-acetylguanine about 30 potential virostatics e.g. I and II
[R1 = H, OH, NH2, SH, Cl, NHAc, OAc; R3 = H, CH2CH(OH)CH2OH; R2, R4 = H, Ac] were prepd.. The syntheses
involved blocking of OH groups yielding Ac or isopropylidene derivs. and numerous substitution and(or) condensation
reactions. None of the compds. prepd. inhibited in concns. <1 mg/mL medium the growth of Escherichia coli. The
antiviral effects will be described elsewhere.
~16 Citings
483. Synthesis of 4-O-methyl-N-acetylneuraminic acid. Part I. Acetonation of 3-acetamido-3-deoxy-D-glycero-D-

galacto-heptose diethyldithioacetal
By Beau, Jean Marie; Sinay, Pierre
From Carbohydrate Research (1978), 65(1), 1-10. Language: French, Database: CAPLUS, DOI:10.1016/S0008-
6215(00)84207-X
Treatment of 3-acetamido-3-deoxy-D-glycero-D-galacto-heptose di-Et dithioacetal with Me2CO in the presence of CuSO4
and traces of H2SO4 gave 3-acetamido-3-deoxy-6,7-O-isopropylidene-D-glycero-D-galacto-heptanose di-Et dithioacetal
in cryst. form and 85% yield. Its structure was ascertained by the synthesis of various derivs. and a study of the
periodate oxidn. of 3-acetamido-1,3-dideoxy-6,7-O-isopropylidene-D-glycero-D-galacto-heptitol. 3-Acetamido-3-deoxy-
4,5:6,7-di-O-isopropylidene-D-glycerol-D-galacto-heptanose di-Et dithioacetal was obtained in excellent yield when
acetonation was performed in the presence of a high concn. of H2SO4 (7%). Its structure was ascertained by periodate
oxidn. of the derived 3-acetamido-3-deoxy-4,5:6,7-di-O-isopropylidene-D-glycero-D-galacto-heptitol. It was converted by
acidic hydrolysis to 3-acetamido-3-deoxy-4,5-O-isopropylidene-D-glycero-D-galacto-heptose di-Et dithioacetal.
~2 Citings
484. Protected graft copolymers of cyclic nitrogenous and ester monomers

By Schwartz, Nelson N.
Unsatd. diesters are free-radically polymd. with N-contg. cyclic monomers in the presence of polyether polyols and the
products are capped by acid anhydrides, isocyanates, vinyl ethers, or carboxylic acids to give copolymers useful as
stabilizers for foams prepd. from isocyanate-contg. formulations. Thus, a soln. contg. azobisisobutyronitrile 2.25, tert-Bu
perbenzoate 0.75, and di-Bu maleate 120g and 66 g N-vinyl-2-pyrrolidone were added in 2 h to 560 g Polyglycol 15-200
(mol. wt. 2600, prepd. by oxypropylation and oxyethylation of glycerol). After the 2 h addn. period, the temp. was raised
to 110° for 1 h, and then 70 g Ac2O was added. An exothermic reaction occurred during this capping operation, and the
mixt. was stirred for an addnl. 3 h at 140°/25 mm to give an acetylated product with end-capping degree >93% and mol.
wt. ∼3600.
~3 Citings
485. Preshaving composition

By Horino, Masaaki; Kato, Seiji
Preshaving compns. for use in elec. razor shaving contain ≥1 compds. with m.p. 30-40° (myristyl cetylate, sucrose fatty
acid esters, cetyl lactate, glycerol trilaurate, decanoyl myristate, ethylene glycol distearate, ethylene glycol decanoate,
cocoa butter, myristyl myristate, acetylated sorbitan palmitate, acetylated glycerol monopalmitate, stearic acid Et ester)
and ≥1 of porous substances (talc, CaCO3, MgCO3, polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl
chloride, nylon, starch, CaHPO4, etc.). For example, a powder preshaving compn. consists of talc 79, glycerol trilaurate
6, microcryst. cellulose 3, silk powder 6, powd. nylon 5, menthol 0.1, Me glycyrrhetinate 0.1, perfumes 0.5, and
hydroxyphenylethylamine 0.3 wt.%. The mixt. was thoroughly blended and sieved to give a powder product with particle
size <100 mesh.
~4 Citings
486. Preparation of hard porous chewing gum

By Yamada, Tetsuji; Fukuda, Masayoshi; Miyaaki, Toru
Elastic, but hard candy materials and gum bases are mixed, melted, and kneaded at a high temp. (55-100°), with stirring
to form hard and porous chewing gum. The hard candy materials consisting of sucrose, glucose or millet jelly, and EtOH
and the gum base is a resin prepn. contg. wax, emulsifier, and inorg. fillers. The optimal ratios between the hard candy
material and gum base are 60-80% to 20-40% by wt. Thus, sucrose 600, millet jelly 400, and water 200 parts were
mixed and heated at 115° to form a hard candy material contg. 2.5% water. The gum base was prepd. by melting and
kneading a mixt. consisting of poly(vinyl acetate) 2%, polybutene 50, polyisobutylene 80, resin glycerol ester 280,
microcryst. wax 80, acetylated monoglyceride 60, and talc 160 parts. To 390 part of preheated (125°) hard candy
material was mixed 140 part gum base preheated to 120°; 3 parts each of citric acid and lemon flavoring material were
then added to the mixt. and stirred at 60-70°. The final mixt. was molded in a spherical shape and dried at 750 mm and
25°. The gum had excellent flavor, texture, and chewing durability.
~0 Citings
487. Plasticizing effect of acetylated castor oil on castor oil-based, moisture-cured polyurethane film
By Mukherjea, R. N.; Saha, K. K.; Sanyal, S. K.
From Journal of the American Oil Chemists' Society (1978), 55(9), 653-6. Language: English, Database: CAPLUS,
DOI:10.1007/BF02682453
Polyurethane films prepd. from castor oil-based polyols are rigid, and some are brittle, esp. those prepd. from ethylene
glycol monoricinoleate [106-17-2] and propylene glycol monoricinoleate [26402-31-3]. Films prepd. from castor oil as
such show some flexibility with elasticity and high elongation. Acetylated castor oil (10-25%) shows a plasticizing effect
when incorporated in castor oil polyols, giving films with good elasticity and flexibility. Films contg. 3-5% triethanolamine
[102-71-6] cured in ∼24 h compared with 3-4 days for films contg. no catalyst. However, the tensile strength and m.p.
were reduced.
~0 Citings
488. Plasticizers for ethylene-vinyl acetate copolymer films

By Yazaki, Takao; Noro, Masataka
Polyolefins are plasticized with glycerol esters of >40 mol% acylated 12-hydroxyoleic acid or 12-hydroxystearic acid.
Thus, a compn. of Yukalon EVA 41 H (ethylene-vinyl acetate copolymer) [24937-78-8] 95.7, sorbitol fatty acid esters 1.3,
and 100% acetylated castor oil 3.0 parts was extruded at 145° into a tubular film and blown 500%. The film had 50%
modulus 105 and 53 kg/cm2 in and across the machine direction, resp., 100% modulus 132 and 69 kg/cm2, resp., 150%
modulus 149 and 76 kg/cm2, resp., tensile strength 238 and 232 kg/cm2, resp., and tensile modulus 490 and 530 kg/cm2,
resp., compared with 82, 48, 106, 63, 122, 73, 226, 215, 540, and 585, resp., for a similar film without acetylated castor
oil.
~0 Citings
489. Nourishing night cream

By Speteanu, Rozalia; Brad, Ion; Petrescu, Mioara; Cismaru, Stanca
From Rom. (1978), RO 65015 A2 19790215, Language: Romanian, Database: CAPLUS
A compn. contg. polyethylene glycol monooleate, lanolin, petrolatum, branched fatty acid esters, liq. lanolin, glycerol,
acetylated liq. lanolin, cetyl alc., lanolin alc., water, preservative, oil-sol. Hippophae rhamnoides ext., water-sol. H.
rhamnoides, and perfume was prepd. and is useful as a nutritive night cream.
~0 Citings
490. Heterocycles from carbohydrate precursors. Part XII. On the ring transformation of hydrazine derivatives
of L-ascorbic acid into nitrogen heterocyclic derivatives
By El Ashry, El Sayed H.; El Kilany, Yeldez; Singab, Farrag
6215(00)84129-4
L-Threo-2,3-hexodiulosono-1,4-lactone 2-(p-methoxyphenylhydrazone) (I) was condensed with arylhydrazines to give
mixed bishydrazones, whose acetylation gave the corresponding di-O-acetyl derivs. I undergoes elimination of one mol.
of water per mol. during the acetylation, and gives 4-(2-acetoxyethylidene)-4-hydroxy-2,3-dioxobutano-1,4-lactone 2-(p-
methoxyphenylhydrazone), which reacts with MeNHNH2, via a ring transformation process, to give 1-methyl-3-(1-
methylpyrazolin-3-yl)-4,5-pyrazoledione 4-(p-methoxyphenylhydrazone). Alkali rearranged the mixed bishydrazones to
1-aryl-3-(L-threo-glycerol-1-yl)-4,5-pyrazoledione 4-(p-methoxyphenylhydrazones), which gave triacetyl and tribenzoyl
derivs., and, upon periodate oxidn., afforded 1-aryl-3-formyl-4,5-pyrazolediones 4-(p-methoxyphenylhydrazone) that gave
the corresponding phenylhydrazones. The NMR and mass spectra of some of these derivs. have been investigated.
~4 Citings
491. Heterocycles from carbohydrate precursors. Part XI. Transformation of the hydrazones of 6-chloro-3-(L-
threo-2,3,4-trihydroxy-1-oxobutyl)-2-quinoxalinone into other heterocyclic compounds
By El Ashry, El Sayed H.; Abdel Rahman, Mohamed M. A.; Nassr, Mahmoud A.; Amer, Adel
6215(00)84128-2
The difference in reactivity of the two amino groups in 3,4-(H2N)2C6H3Cl allowed it to react with L-threo-2,3-
hexodiulosono-1,4-lactone to give, after further reaction with various hydrazines, quinoxalinones I (R = 4-R1C6H4, 4-
R2C6H4CO; R1 = Me, OMe, Br, I, NO2, SO2NH2, R2 = H, Me, Cl, I), whose structures were deduced from their reactions,
as well as from mass spectrometry of the p-nitrophenylhydrazones. Elimination of one mol of water per mol from these
hydrazones gave the 1-aryl-6-chloro-3-(L-glycerol-1-yl)flavazoles; the mass spectrum of one of these flavazoles is
discussed. Elimination of two mols of water per mol from I (R = C6H4Me-4, C6H4Br-4, C6H4I-4) occurred with
simultaneous cyclization to give 3-[1-aryl-5-(hydroxymethyl)pyrazol-3-yl]-6-chloro-2-quinoxalinones, whose acetylation
gave the corresponding monoacetyl derivs. that could also be obtained by the action of boiling Ac2O on the starting
hydrazones. Periodate oxidn. of the hydrazones and the flavazole derivs. afforded the corresponding aldehydes.
~4 Citings
492. Fungicidal and bactericidal heterocyclic derivatives of 1(1,3-dioxolan-2-ylmethyl)-1H-imidazoles and -1H-

1,2,4-triazoles
By Heeres, Jan; Backx, Leo J. J.; Mostmans, Joseph H.
The title compds. I (X = CH, N; R = Ph, optionally substituted by 1-3 halogen, lower alkyl, alkoxy; R1 = pyrazolyl,
optionally substituted pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl, or tetrazolyl). Thus, II and 4-(2-phenyl-1H-imidazol-1-
yl)phenol Na salt (III) reacted to give 55% I (X = CH, R = 2,4-Cl2C6H3, R1 = 4-imidazolyl) which was effective against
vaginal candidiasis in rats at 1.25 mg/kg. III was prepd. by treating 2-phenylimidazole with 4-MeOC6HBr to give 1-(4-
methoxyphenyl)-2-phenylimidazole which was demethylated with HBr and treated with NaOH to give III.
~4 Citings
493. Fungicidal and bactericidal 1-(1,3-dioxolan-2-ylmethyl)-1H-imidazoles and -1H-1,2,4-triazoles and their salts
By Heeres, Jan; Backx, Leo J. J.; Mostmans, Joseph H.
The title compds. I (X = N, CH; R = Ph, optionally substituted by 1-3 halogen, lower alkyl, alkoxy; R1 = NCS, NH2,
substituted amino, carbamate, thiocarbamate, ureido, thioureido, heterocyclic amino; R2 = H, NO2) were prepd. Thus I
(X = CH, R = 2,4-Cl2C6H3, R1 = 4-NHBz, R2 = H; II) was obtained in 51% yield by treating III with 4-HOC6H4NHBz. II
was effective against vaginal candidiasis in rats at 2 × 5 mg/kg orally.
~25 Citings
494. Enterobacterial common antigen: isolation from Shigella sonnei, purification and immunochemical
characterization
By Lugowski C; Romanowska E
From European journal of biochemistry (1978), 91(1), 89-97, Language: English, Database: MEDLINE
In the studies presented the effective procedure of isolation and purification of enterobacterial common antigen from
Shigella sonnei has been elaborated. The method is based on sonification of bacterial suspension in the presence of
lysozyme and EDTA and subsequent extraction of the pellet with boiling water. The crude extract of common antigen
was purified by fractionation with ethanol and chromatography on silica gel and Sephadex LH-20. The comparison of
several extraction procedures of enterobacterial common antigen from Shigella sonnei proved that the method
described above is most effective. The purified enterobacterial common antigen preparation obtained preserved full
biological activity: antigenicity (precipitation and activity in enzyme-linked immunosorbent assay), immunogenicity in
rabbits, ability to coat erythrocytes (passive hemagglutination) and inhibitory activity in passive hemagglutination. The
pure enterobacterial common antigen was identified to 90% as a polymer of N-acetyl-D-mannosaminuronic acid and N-
acetyl-D-glucosamine (2:1, molar ratio), O-acetylated and containing 3.2% fatty acids (C16:0 and C18:1, not oleic). It
contains 5.3% nitrogen, less than 4% protein, less than 0.5% phosphorus and less than 1.6% neutral sugar; glycerol
and RNA were not found in the preparation.
~11 Citings
495. Enterobacterial common antigen: isolation from Shigella sonnei, purification and immunochemical
characterization
By Lugowski, Czeslaw; Romanowska, Elzbieta
From European Journal of Biochemistry (1978), 91(1), 89-97. Language: English, Database: CAPLUS,
DOI:10.1111/j.1432-1033.1978.tb20941.x
The isolation and purifn. of enterobacterial common antigen from S. sonnei has been elaborated. The method is based
on sonification of bacterial suspension in the presence of lysozyme and EDTA and subsequent extn. of the pellet with
boiling water. The crude ext. of common antigen was purified by fractionation with EtOH and chromatog. on silica gel
and Sephadex LH-20. The comparison of several extn. procedures of enterobacterial common antigen from S. sonnei
proved that the method described above is most effective. The purified enterobacterial common antigen prepn. obtained
had full biol. activity: antigenicity (pptn. and activity in enzyme-linked immunosorbent assay), immunogenicity in rabbits,
ability to coat erythrocytes (passive hemagglutination), and inhibitory activity in passive hemagglutination. The pure
enterobacterial common antigen was identified to 90% as a polymer of N-acetyl-D-mannosaminuronic acid and N-acetyl-
D-glucosamine (2:1, molar ratio), O-acetylated and contg. 3.2% fatty acids (C16:0 and C18:1, not oleic). It contains 5.3%
N, <4% protein, ≤0.5% P, and ≤1.6% neutral sugar; glycerol and RNA were not found in the prepn.
~15 Citings
496. Directly synthesizable mixture of cyclic acetals used in lacquers and paints
By Blaga, Aurel Ioan Stefan; Ferenczi, Stefan; Pape, Richard Francisc; Vincze, Martin Antoniu; Vladea, Radu Valentin;
Chirila, Traian Vasile
From Rom. (1978), RO 63233 A2 19780228, Language: Romanian, Database: CAPLUS
A mixt. contg. 4-hydroxymethyl-2-isopropyl-1,3-dioxolane [31192-94-6] and 5-hydroxy-2-isopropyl-1,3-dioxane [4877-
28-5], useful as a solvent for varnishes and paints manufd. from, e.g. nitrocellulose, is manufd. by reaction of glycerol [
56-81-5 ] with isobutyraldehyde [78-84-2] in the presence of K sulfate in PhMe at 80-135°.
~1 Citing
497. Cyclic ketals. 9. Condensation products of benzaldehyde and alpha-monothioglyerol

By Bohm R
From Die Pharmazie (1978), 33(7), 465-6, Language: German, Database: MEDLINE
~0 Citings
498. Two-year oral toxicity and multigeneration studies in rats on two chemically modified maize starches
By Truhaut, R.; Coquet, B.; Fouillet, X.; Galland, D.; Guyot, D.; Long, D.; Rouaud, J. L.
From Food and Cosmetics Toxicology (1979), 17(1), 11-17. Language: English, Database: CAPLUS,
DOI:10.1016/0015-6264(79)90152-4
No effects of toxicol. importance were obsd. during the feeding of 2 modified maize starches, acetylated distarch adipate
[63798-35-6] and acetylated distarch glycerol [53123-84-5], each at 62% in a cooked diet, to Sprague-Dawley-derived
rats throughout a 2-yr oral toxicity study and multigeneration study (3 generations over ∼2 yr).
~4 Citings
499. Toxicity of rac-1(3)-palmitoyl glycerol in weanling mice

By Schnitzer-Polokoff R; Tove S B
From The Journal of nutrition (1979), 109(8), 1358-67, Language: English, Database: MEDLINE
Reinvestigation of the previously reported toxicity of saturated fat on weanling mice has shown rac-1(3)-palmitoyl
glycerol to be a more potent toxic agent than free palmitic acid when fed as the sole source of dietary fat. As shown
before, protection against this toxicity can be afforded by the addition of 2 to 4% safflower oil. We have now shown
that if the rac-1(3)-palmitoyl glycerol is acetylated the toxicity is much less. The protective effect of diacetyl rac-1(3)-
palmitoyl glycerol cannot be totally ascribed either to the presence of acetate itself or to the blocking of the free
hydroxyls of palmitoyl glycerol by acylation. In vivo absorption studies coupled with in vitro experiments with
pancreatic lipase suggest that the major protective effects result from increased lipolysis of the acylated palmitoyl
glycerol, causing conversion to the less toxic free palmitic acid.
~1 Citing
500. Toxicity of rac-1(3)-palmitoyl glycerol in weanling mice

By Schnitzer-Polokoff, Robin; Tove, Samuel B.
From Journal of Nutrition (1979), 109(8), 1358-67. Language: English, Database: CAPLUS, DOI:10.1093/jn/109.8.1358
Reinvestigation of the previously reported toxicity of satd. fat on weanling mice showed rac-1(3)-palmitoylglycerol [542-
44-9] to be a more potent toxic agent than free palmitic acid when fed as the sole source of dietary fat. Protection
against this toxicity was afforded by the addn. of 2-4% safflower oil. If the rac-1(3)-palmitoylglycerol were acetylated, the
toxicity was much less. The protective effect of diacetyl rac-1(3)-palmitoylglycerol [55268-70-7] could not be totally
ascribed either to the presence of acetate itself or to the blocking of the free hydroxyls of palmitoylglycerol by acylation.
In vivo absorption studies coupled with in vitro expts. with pancreatic lipase suggested that the major protective effects
resulted from increased lipolysis of the acylated palmitoylglycerol, causing conversion to the less toxic free palmitic acid.
~0 Citings

Glycerol Acetylation 1

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Glycerol Acetylation 1

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1. Partially acetylated polyhydroxylic compounds

2. Estimation of glycerol in soap lyes and crude glycerol

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4. Investigations over the secretions. [machine translation]

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5. To the Glycerin determination in the wine. [machine translation]

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8. About the tribasic alcohol from Allyldipropylcarbinol. [machine translation]

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9. The theory of saponification. [machine translation]

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13. About the Allylmethylphenylcarbinol. [machine translation]

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15. About nitro compounds of the Anthragallols. [machine translation]

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16. Quantitative experiments with the fermentative lipolysis. [machine translation]

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18. Over Caryophyllin. [machine translation]

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27. Ricinstearolic Acid

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28. Analysis of Fats

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29. Chemistry of starch. II. Schardinger's crystallized dextrins

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30. Alfalfa. VI. Alfalfa seed oil

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32. Modifying solubilities of acetylcellulose

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33. The specific gravity and index of refraction of glycerol solutions

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34. Tannin and the synthesis of similar substances. VI

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35. Plastic mixtures

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36. Note on a deposit in refined soy bean oil

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37. Japanese peppermint

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38. Transpositions in the camphene series. II

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39. The cocorice

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40. Proso millet investigations-analysis of the oil-a characteristic alcohol

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41. Synthesis of fatty acid derivatives of the sugars. I

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