149

Organic Chemistry.
Oxidation of U n s a t u r a t e d Compounds by means of
LIPPMANN
(Ber., 1910, 43, 464.
Organic Peroxides. EDUARD
Compare PrileschaBeff, this vol., i, 86)-The
addition of benzoyl
peroxide to amylene, and the subsequent hydrolysis to isodiamylene
oxide, was studied by the author in 1884 (Abstr., 1885, 366).
J. J. 5.
Condensation of sec.-Butyl A l c o h o l with its Sodium
Derivative. MARCELGUERBET(Compt. rend., 1910, 150, 183-1 85.
Compare Abstr., 1902, i, 130, 583, 6 5 7 ; 1908, i, 162, 635).-When
see.-butyl alcohol is heated with its sodium derivative a t 200-220"
there is formed a mixture of two alcohols : (1) y-Methylheptun-E-ol,
CHMeEt*CH,*CHEt*OH, a liquid with a mint-like odour, has
b. p. 167-169O (corr,), DO 0,8493; its acetate has b. p. 283-185"
(corr.). On oxidation, the alcohol yields y-methylheptccn--one,C,H,,O,
b. p. 161' (corr.) ; the semicarbaxone crystallises in needles, m. p. 96'.
The constitution of the foregoing alcohol and ketone was deduced
from a study of their oxidation products.
(2) The dodecyl alcohol, '' trisec.-butylic alcohol," C,,H,,O, b. p.
250-255'
(corr.), a n agreeably smelliug liquid, is converted 011
oxidation into t h e corresponding ketone, C,,H,,O, b. p. 247-24s'
(corr.). This forms a semicarbaaone, m. p. 161-162'.
W. 0. W.
M e t h y l a c e t e n y l c a r b i n o l [Butinene-7-011. ROBERTLESPIEAU
Compare Abstr., 1908, i, 496).
-A description of a method for preparing alcohols of the type
O H C H R *CiCH. P-Bromo-Aa-butevbe-y-ol, O H *C B Me-CBr :CH,, o btained by the action of magnesium methyl iodide on bromoacraldehyde, is a colourless liquid, b. p. 59.5-60'/14
mm., or 1 5 1 O j
732 mm. (decornp.); it forms a pheizyllurethane, m. p. 63*5--63.5'.
Alcoholic potassium hydroxide converts the alcohol almost quantitatively into acetylene, whilst the aqueous alkali brings about a more
complex change. Amongst t h e products recognised were acetylene,
yropionic acid, and butinene-y-ol, OH*CHMe*CiCH. This was isolated,
mm. By
not quite free from water, as a liquid, b. p. 107-109'/760
treating with a n ammoniacal cuprous chloride solution, a precipitate
is formed, which, on treatment with iodine and potassium iodide, is
converted into aap-tri-iodo-La-butene-y-oZ,OH*CHMe*CI:CI,, m. p. 96".
w. 0.
(Compt. rend., 1910, 150, 113-114.

w.

U n s a p o n i f i a b l e C o n s t i t u e n t s of Japan Tallow. HERMANN

MATTHESand W. HEINTZ(Arch. Pharm., 1909, 247, 650-657)J a p a n tallow, m. p. 53-53-5, D 1.0038, is saponified by alcoholic
potassium hydroxide, and t h e clear soap solution is diluted with water
and extracted with ether. The residue obtained by the distillation of
VOL. XCVILI. i .
m

i. 150

ABSTRACTS OP CHEMICAL PAPERS.

the ethereal extract is submitted to a repetition of these operations.

The final residue thus obtained in 0.68% yield is a yellowish-brown
mass (iodine number 36*25),which is separated by petroleum into a n
insoluble portion, from which myricyl alcohol is isolated, and a
soluble portion, from which phytosterol, m. p. 139O, and ceryl alcohol,
m. p. 79O,are obtained, together with a saturated ulcol~ol,m. p. 65'
(ucetate, m. p. 41), which is probably nonadecyl alcohol, C,,H4,0.

c. s,

Dimethyldiethyldicarbinol [yS - Dimethylhexane - y8 - diol].

Mlle, CECILEFRUMINA
(Bull. Acud. roy. Belg., 1909, 1151-1 157).Lawrinowitsch's pinacone, obtained by reducing methyl ethyl ketone
with sodium (Abetz., 1877, ii, 427), lists been prepared by the action
of magnesium ethyl iodide on methyl oxalate, and proved to consist
of a single liquid substarice, y&dirnethylhexane-y8-diol,
OH*CMeEt*CMeEt.OH,
b. p. 195'/760 nim. or 10/l10 mm. The solid modification obtained
by Zelinsky and ICrapiwin (Abstr., 1893, i, 390) in repeating
Lawrinowitsch's experiment was not produced in the synthesis now
described. The diethyl ether has b. p. 142-143'/760
mm. or
110-111'/20
mm., and is liquid. The dichloride boils at 165-166"/
760 mm. or at 114-115/18 mm.
T. A . H,
Drying of Moist Ether. E. VON SIEBENROCK
(Monatsh., 1909,
30, 759-'766).-A
comparative study of calcium chloride, potassium
carbonate, sodium sulphate, magnesium sulphate, sylvite, potassium
chloride, calcium sulphate, and carnallite, having regard to their use,
i n the anhydrous state, for the removal of water from moist ether.
The first two substances mentioned are shown to be most efficacious;
sodium sulphate, a substance frequently recommended and used for
drying ether, is not very effective, and may be replaced with great
advantage by carnallite and magnesium sulphate.
W. H. G.
Action of Sulphur and Ammonia on Organic Sulphides
(Bey., 1910, 43, 220-226.
and Disulphides. BRORHOLMBERG.
Compare Abstr., 1908, i, 308).-0rganic
sulphides and disulphides
form reddish-brown additive products of the general formula
R,S,,yNH, with sulphur and ammonia. The reaction is reversible, the
equilibrium depending on the sulphide used. I n some cases, as with
ethyl and p-tolyl disulphides, the additive product undergoes further
change into the tetrasulphide, according t o the equation :
R,fLyNH, t
:R p , t ss-4 + yNH,,
so that the ammonia can be considered to act catalytically on the
formation of tetrasulphides from disulphides and sulphur.
The organic sulphide or disnlphide is dissolved in absolute alcohol,
a n excess of flowers of sulphur added, and the solution then saturated
with ammonia, whereby the colour gradually changes t o a dark brown.
After some weeks the undissolved sulphur is collected and weighed,
the filtrate allowed to evaporate spontaneously, and the residue then
investigated.
With ethyl sulphide, the residue consisted of a minute trace of
sulphur, but the additive product must have been formed in solution,

i. 151

ORGANIC CHEMISTRY.

since the presence of ethyl sulphide is necessary for the formation of

the brown colour.
Ethyl disulphide gave a residue of a yellow uncrystallisable oil;
when this was distilled under diminished pressure (1 2 mm.), a colourless liquid distilled over a t 77-78',
and the residue in the flask
consisted of ethyl tetrasulphide.
p-Tolyl disulphide (prepared from p-tolyl mercaptan and sulphuryl
chloride in ethereal solution, or by the spontaneous oxidation of an
alkaline solution of the mercaptan) gave a solid residue, contaminated
with oil, which after recrystallisation from alcohol is found t o be a
mixture of the di- and tetra-sulphide, the latter having rn. p. 75".
Diethyl dithiodiglycollate gave a dark-coloured solution, from which
the original substances were always regenerated, no matter what the
treatment ; large quantities of sulphur dissolved. If the filtrate,
after collecting the excess of sulphur, was again saturated with
ammonia and kept for six weeks, the amide, m. p. 156-157", derived
from the original ester was formed.
I n a n appendix on the inorganic polysulphides, the author states
his opinion that compounds with simple sulphur chains are colourless,
or only pale yellow ; a brown colour is due to the presence of larger
atomic complexes, S,. Whether the compound should be formulated
T.S. P.
is left undecided.
as M,S,S, or R!I2S2,SZ

Crystalline Form and Optical Characters of Lead

(Centr. Min., 1910, 17--24).--Crystals
Formate. B. KARANDEEFF
of lend formate, Pb(CHO,),, are orthorhombic, with cc : b : c =
0.T4538 : 1 : 0.84656. Detailed determinations of the optical
constants are given.
1,. J. 8.

KAUFLER
(Bey., 1910,
[Electrolysis of Carboxy-acids.] FELIX
43,266).-The statement made by the author and C. Herzog (Abstr.,
1909, i, 870) i n connexion with the attitude of Forster and Piguet
(Abstr., 1904, i, 965) towards the superoxide theory was incorrect.
A n error was also made in the reference to the work of Xiller and
Hofer.
R. V. S.

Formation of Dichloroacetic Acid from Trichloroacetaldehyde by Wallach's Method. ARTHURKOTZ(Festsciwift Otto

WaEZach, 1909,496--501. Compare Wallach, a b s t r . , 1578, 283, 2SS).The conversion of chloral into dichloroacetic acid, which may be
brought about through the agency of water alone, is greatly facilitated
by the presence of potassium cyanide, probably owing to the intermediate formation of chloralcyanohydrin, CCI,*CH(OH)*CN, and
aa-dichloro-~-cyano-/3-hydroxyethylene,CCI,:C(OH).CN,
or the
tautomeride, dichloropyruvonitrile, CHCI,*CO*CN. The following
observations are quoted in support of this explanation : (1) Dichloroacetic acid is formed by the action of water on chloralcyanohydrin.
(2) Nitriles of dihalogenated pyruvic acids under the conditions of
Wallach's method yield dihalogenated acetic acids and hydrogen
cyanide. (3) Trichlorolactic acid may be converted in aqueous solution into dichloroacetaldehyde, hydrogen chloride, and carbon dioxide j

m 2

i. 152

ABSTRACTS OF CHEMICAL PAPERS.

this reaction undoubtedly takes place through the intermediate

formation of aa-dichloro-P-hydroxyethylenecarboxylicacid or t h e
tautomeric dichloropyruvic acid, since dihalogenated pyruvic acids
decompose in aqueous solution, yielding dihalogenated aldehydes and
carbon dioxide.
Chloroacetaldehyde and dicliloroacetaldehyde behave similarly to
chloral, with the difference that the first-named substance cannot be
converted into formic acid and chloromethane.
/3-Halogenated aldehydes, such as P-chloropropaldehyde, cannot be
converted into t h e corresponding acids even under t h e influence of
hydrogen cyanide ; it would appear, therefore, t h a t reactions of the
nature under discussion only take place when halogen and oxygen are
united t o adjacent carbon atoms.
W. H. G.

Catalytic Phenomena. JACOBBOESEKEN(Proc. K. Akud.

Vetensch. Amsterdam, 1909, 12, 417-421).-By
the researches of
Perrier (Abstr., 1900, i, 331) and the author (Abstr., 1900, i, 349 ;
1901, i, 474) it has been shown that i n Friedel and Crafts' reaction it
is not the aromatic hydrocarbon, but the chloride or anhydride, which
is first attacked by the aluminium chloride, a s in many cases additive
products can be isolated. The author regards this initial action a s
consisting of a loosening of the chloride, and possibly also of the
double linkings of the benzene derivative, it being known that many
reactions indicate the action of aluminium chloride t o be purely a
dissociating one. I n order to test this view, the author has examined
several additional cases, and with the idea t h a t the reaction might
proceed more readily if stable chlorine compounds, such as hydrogen
chloride, could be formed during the decomposition, the substances
chosen were trimethylacetyl chloride, dichloroacetyl chloride, chloral
and trichloroacetyl chloride; these all contain a more or less overloaded carbonyl group, so t h a t the reaction could be followed by the
evolution of carbon monoxide. The results obtained are as follows :
Trimethylacetyl chloride is resolved a t 0' according to the equation
CMe,*COCl= HC1+ CO + C,H8, the isobutylene being almost entirely
poly merised, When gently heated, chloral undergoes decomposition i n
two directions : ( a ) CCl,*CHO = HC1+ CO + CCI, (or C,Cl,), to the
extent of 70-75% ; and (6) CCl,*CHO = CO + CHCl,. W i t h dichloroacetyl chloride decomposition takes place in the two directions :
CHCI,*COCl = CO + CHCl,, to 60%, and CHCl,*COCl= CO + HC1+ CCI,,
the CCl, presumably being polymerised t o C , a , o: lrichloroacetyl
chloride, when repeatedly distilled with aluminium chloride, is
decomposed in one direction : CCl,*COCl= CC1, + CO.
It is remarkable that, i n spite of its excess of chlorine atoms,
trichloroacetyl chloride is the most difficult of attack. The reaction
seems t o proceed particularly smoothly in the case where hydrogen and
chlorine atoms are united with two adjacent carbon atoms.
The course of the reaction with chloral and dichloroacetyl chloride
indicates t h a t it is the movable chlorine atom which is initially
rendered active. The action of aluminium chloride on trimethylacetyl chloride is too violent t o admit of the first stage of the reaction
being ascertained. B u t with sulphuric acid, which in many cases

i. 153

ORGANIC CHEMISTRY.

behaves analogously to aluminium chloride and forms the same kind

of additive products, the reaction appears to pass through the phaves :
CMe,*COCl + H,SO, = CMe,*CO*SO,H + HC1 and CMe,*CO-SO,H =
H,SO,+CO+C,H,,
the chlorine atom being first detached by the
sulphuric acid.
T. H. P.
Detergent Action of Soap Solutions. 111. W A L T H ~SPRTNG
RE
(Bull. Acad. my. Belg., 1909, 1059-1065 ; Arch. Sci.phys. nat., 1910,
china. Belg., 1910, 24, 17-54.*
Com[iv], 29, 42-43, and BUZZ. SOC.
pare Abstr., 1909, i, 625, and this vol., i, 6).-The results obtained
with '' red ochre " (loc. cit.) have led to the extension of t h i s investigation to the action of hydrated alumina on soap solutions, The results
are analogous to those obtained with red ochre.
To each member of a series of fourteen solutions containing quantities
of soap ranging from 1/2.5% to 1/16%, 2 C.C. of a mixture of water and
aluminium hydroxide (equivalent to 0.0061% A1,0,) were added. The
mixtures containing 1/8%and 1/16% of soap flocculated in twenty-four
hours, and that containing 1/4% of soap flocculated in thirty-nine hows ;
the remaining mixtures, except that containing l/2.5% soap, having in
this time flocculated partially. Changes in the relative proportions of
aluminium hydroxide and soap displace these points of flocculation,
and also mask the periodicity. The coagulated product is pulverulent,
like that obtained with ferric hydroxide (Zoc. cit.), and on ignition gives
a mixture of about 3 mols. of alumina to 1 mol. of sodium carbonate,
indicating an original adsorption product of 3 mols. of alumina with
T. A. H.
2 of soap.

Detergent Action of Soap Solutions. IV. W A L T H ~SPRING

RE
(Bull. Acad. roy. Belg., 1909, 1128-1139, and BUZZ.Soc. chim. Belg.,
1910, 24, 17-54 *).--Silicic acid, clay, and cellulose react with soap
solutions in the same may as lampblack (Abstr., 1909, i, 628), red
ochre (this vol., i, 6) and alumina (preceding abstract) forming with
a part of the soap insoluble adsorption compounds, which are less
adhesive than the original colloidal substances.
A soap solution in which silicic acid has been suspended, and which
has been clarified by deposition, does not redden with phenolphthalein
solution, and yields less alkaline ash on evaporation and ignition than
the original solution, due to combination OF the silicic acid with a
basic portion of the soap. Such a suspeiision on filtration yields a
filtrate containing silica, and the amount of the latter i n the filtrate
augments with the diminution in concentration of the soap solution
(compare Zoc. cit.). Solutions of soap of strengths varying from
1/512% to 2% show periodicity in suspending power for silicic acid, the
maxima being at about 1/16% and 1/2%, and the minimum a t about
1/8%.
Pottery clay behaves in a similar manner. Its suspension in soap
solution of any strength clears with difficulty, but a maximum
suspending power is shown by a soap solution of 1/8% strength.
After ignition, the clay decomposes soap less readily, and deposits much
more easily from suspensions, the maximum suspending power for
baked clay being shown by a soap solution of 1/32% strength.

* The last reference contains the complete paper,

Parts 1-11'.

i. 154

ABSTRACTS OF CHEMICAL PAPERS,

Cellulose has no effect on soap in solutions containing less than 1%,

but for concentrations above this the soap is decomposed, a basic
T. A. H.
portion combining with the cellulose.

Xanthic Acid and Dixanthogen [Ethyl Di-oxythiocarbonate].

11. MANFRED
RAGG
(Chem. Zeit., 1910,34, 82-84.
Compare Alostr.,
1908, i, 604).-A pure xanthate can only be prepared when water is
excluded from the reaction mixture in order t o prevent hydrolysis. To
prepare sodium xanthate, sodium is dissolved in excess of ethyl alcohol,
and then the calculated quantity of carbon disulphide added, the
reaction mixture being stirred and cooled meanwhile. The solutioa
so obtained is fairly stable, and gives a yellow precipitate with copper
salts which is free from the dark brown impurities which are formed
when hydrolytic products are present. The yellow precipitate consists
of cuprous xanthate and ethyl di-oxythiocarbonate, the reaction taking
place quantitatively according to the equation : 4NaS*CS*OEt +
2CuS0, = Cu,(S-CS-OEt), + S,(CS*OEt), + 2Na,SO,.
The dixanthogen
can be extracted from the precipitate by means of carbon tetrachloride.
It is noteworthy that if sodium is added to a mixture of ethyl alcohol
and carbon disulphide, sodium xanthate is not formed, but a compound
which gives a dark red precipitate with copper salts, and only changes
into yellow cuprous xanthnte on warming.
The following dixanthogens [di-oxythiocarbonates] and xanthates
have been prepared in a similar manner from the correspouding
alcohols :
Methyl di-oxythiocarbomate,S,(CS*OMe),, is a brownish-yellow, viscid
oil, with an odour different from that of the ethyl compound, and
somewhat similar to that of acetone ; D = 1.180 ; b. p. 128' (decomp.).
Cuprous methyl xantlLate is a pale yellow powder.
n-PropyZ di-oxytl~iocarbonate,S,(CS*OPr),.-Brown
liquid with no
characteristic odour ; D = 1.087 ; b. p. 117" (with decomposition).
Cuprous n-popyl xanthate forms a pale yellow powder.
isoButyl di-oxpthiocarbonate, S,( CS*O*C,H,),,
is a yellow oil ;
D=1.080; b. p. 165". I n the preparation of sodium isobutyl
xanthate, it is necessary to use a large excess of the alcohol and to
warm the reaction mixture. After the addition of the copper salt, the
excess of isobutyl alcohol must be extracted with 40% ethyl alcohol, in
which both the cuprous xanthate and the dioxythiocarbonate are
insoluble. Cuprows isobutyl xanthate is a light yellow powder.
AmyZ di-oxythiocarbonate, S2(CS*0*C5H1&,was prepared from
ordinary commercial amyl alcohol. Dark yellow oil ; D = 1.007; b. p.
158'. Cuprouus amyl xantlLate is pale yellow in colour.
Benzyl di-oxythiocarbonate, S,(CS*O*C7H,,),.-Yellow oil with a
characteristic, but not unpleasant odour ; D = 1.218. Cuprous benxyl
xanthate is coloured pale yellow, and is stable up t o 60'. Sodium
bemzyl xanthate can be recrystallised from alcohol, but the aqueous
solution gradually decomposes.
Attempts t o prepare glycerol derivatives were unsuccessful, although
the results obtained point to the existence of a cuprous glyceryl
monoxanthate.
T. S. P.

ORGANIC CHEMISTRY.

i. 155

Addition of Acid Anhydrides to Aldehydes and Retonee.

RUDOLFWEGSCHETDER
and ERNST SPATH (Monatsh., 1909, 30,
825-869).-Acid
anhydrides, for example, the anhydrides of acetic
acid, propionic acid, chloroacetic acid, and benzoic acid, react with
aldehydes in the presence of sulphuric acid, yielding di-esters of the
aldehyde hydrates ; of all the aldehydes investigated, citronella1 alone
did not behave in this manner, owing to the extreme readiness with
which it, is decomposed by acids. I n the absence of sulphuric acid and
at high temperatures, esters of the enolic form of the aldehyde are
chiefly formed (compare Semmler, Abstr., 1909, i, 364). The mode of
action of the sulphuric acid is not clear; t h a t the mixed anhydride
which is possibly formed is directly concerned in the esterification of
the aldehyde is not probable, for the sulphuric acid may be replaced
by hydrochloric acid, in which case the mixed anhydride is acetyl
chloride, but acetyl chloride reacts with aldehydes, yjelding acetates
ol chlorinated alcoholp and only very small quantities of aldehyde
diacetates. The sulphuric acid may likewise be replaced by nitric
acid, phosphoric acid, or oxalic acid, but not by 3-nitrophthalic acid,
although this is a stronger acid than oxalic acid; possibly the acid, in
this case, is converted into the anhydride, and is thus replaced by
acetic acid,
Attempts to acetylate acetone, acetophenone, and benzophenone
have proved unsuccessful.
The aldehyde diacetates are hydrolysed quite readily by hot water,
and are decomposed by phenylhydrazine, with the formation of
aldehyde phenylhydrazones and up-acetylphenylhydrazine. The dibenzoates are hydrolysed by hot, but not by cold, aqueous potassium
hydroxide.
Certain of the compounds mentioned later are extremely poisonous,
The following compounds, all of which have been prepared by
various investigators in different ways, are readily obtained by the
interaction of the aldehyde and acid anhydride under the influence of
sulphuric acid : methylene diacetate, ethylidene diacetate, heptylidene
diacetate, chloral diacetate, crotonaldehyde diacetate, cinnamylidene
diacetate, ethylidene dipropionate, chloral bischloroacetate, b. p.
168O/10 mm, (compare Gabutti, Abstr., 1900, i, 370), and methylene
dibenzoate. The interaction of salicylaldehyde and acetic anhydride
i n the presence of sulphuric acid leads to the formation of o-acetyloxybenzaldehyde diacetnte ; salicylaldehyde diacetate is not formed, as
stated by Perkin (Annalen, 1868, 146, 371), neither could it be
obtained in t h e manner described by Barbier (Abstr., 1880, 465).
Propylidem diacetate, CfH1204,is a colourless liquid, b. p. 184-1859
(corr.) ; isobutylidene diacetate, C,H,,041 is a liquid with a not
unpleasant odour, b. p. 189' (corr. ) ; benxylzdens dipropionate, C,,Rl6O4,
is a n oil, b. p. 158--159O/lO mm. ; chlorcd dibenxoate, C,,H,,O,C],,
forms large, well-defined, glistening crystals, m. p. 63-45' ;
benaylidene di6enxoate, C,1H1,04, crystallises in long, silky needles,
m. p. 6 1-62O; o-nitrobenxylidene dibenxoate, C,,H1,06N, is dimorphous,
m. p. 123-124'
and 147-148O; it decomposes when distilled in a
vacuum, yielding o-nitrobenzaldehy de and benzoic acid ; m-nitro
benxyliclene dibenxopte farms rosgttes of silky, white crystals, m. p.

i. 156

ABSTRACTS OF CHEMICAL PAPERS.

97-99" ; the para-isomeride has m. p. 118" ; cinnamylidene dibenzoate,

C,,H,,O,, crystallises in needles, m. p. 133-1 35".
Ethyladene dibenzoute, C,,H,,O,,
could not be prepared by the
sulphuric acid method; i t is obtained by the action of benzoic
anhydride on ethylidene diacetate in the presence of a small quantity
of sulphuric acid a t looo, and forms small, glistening crystals, m. p.
70--71".
W . H. G.

Viciaoose, a New Reducing Sugar Containing Cll. GABRIEL

BERTRAND
and GUSTAVE WEISWEILLER
(Compt. end., 1910, 150,
180-182.
Compare Abstr., 1906, i, 6s; 1908, i, 817).-The cyanogenetic glucoside observed by Bruyning (Abstr., 1900, ii, 160) in the
seeds of Vicia angustifilia undergoes hydrolysis when treated with a
diastase occurring in the seeds. A new sugar, uicianose, C,,H,,O,,,
has been isolated from the products of hydrolysis. This is the first
biose isolated from a glucoside. The compound crystallises in spherular
aggregates of small needles; it is very soluble in water, but only
sparingly so in alcohol. A 10% aqueous solution, after fifteen minutes,
shows a$'-%+ 1 5 . 8 O (300 mm. tube), but after twenty-two hours the
rotation remains constant a t
+ 9*32O= + 39.72'. Vicianose has
In. p. about 210; i t has a somewhat higher cupric reducing power
w. 0. w.
than maltose, and is not fermented by yeast.

[.ID

Theory of the Nitration of Cellulose. ALEXIS

V. SAPOSCEINIKOFF

(J.Russ. Phys. Chem. SOC.,

1909, 41, 1712-1741.

Compare Abstr.,
190'7, i, 390).-The
author first discusses the work of previous
investigators on the action of nitric acids cf various concentrations,
either alone or mixed with sulphuric acid, on cellulose.
The non-homogeneity of nitro-cellulose is due largely to the dilution
of the nitrating mixture by the water developed in the reaction, the
external parts of the mass being more highly nitrated than the inner
parts. The final degree of nitration is influenced by the reversibility
of the process. If the uitric acid employed is sufficiently concentrated
to form nitric ethers of cellulose, and if it is in sufficiently great excess,
chemical action proceeds very rapidly. Thus, with a mixture containing 23.8% HNO,, 71.5% H,SO,, and 4.7% water a t ZOO, it was found
that, after two minutes, only 1*S% of the cellulose (cotton) remained
unattacked, the nitrated part containing 12.7% of nitrogen, corresponding with the introduction of 10N0,; after five minutes, 11N0, were
introduced. These results, together with those obtained with a
nitrating mixture composed of 30% HNO,, 65%H2S0,, and 5% H20,
are in accord with those obtained by Lunge and Bebie (Abstr., 1901,

i, 508).
Ternary mixtures of sulphuric and nitric acids and water were
investigated by determining the densities, electrical conductivities, and
partial pressures of the vapours of nitric acid in the mixtures (compare
Abstr., 1904, ii, 251,558, 614 ; 1905, ii, 583). The results obtained
indicate that in such mixtures there occurs a reversible process of the
type : HNO,,nH,O + H,SO, t;HNO,,(rz - x)H,O I- H2S0,,eH,0. This
dehydration of nitric acid reaches a limit with a, mixture of the
composition corresponding with the equntion :

BNO, + x,SO, + xH,O = HNO,

+ x(H,SO,,H,O),

ORGANIC CHEMISTRY.

i. 157

further addition of sulphuric acid resulting in the formation of nitric

anhydride. The results of the investigation of these ternary mixtures
are given in the form of a triangular diagram (compare Abstr.,
1907, i, 390).
The relation between the composition of the nitrating mixture and
the degree of nitration of cellulose is discussed with t h e help of a
large number of numerical results.
T. H. P.

Synthesis of the Phospho-organic Acid of the Seeds

of Plants (Posternak's Anhydroxymethylene-diphosphoric
Acid). ANGELO
CONTARDI
( A t t i R. Accad, Lincei, 1910, [v], 19, i,
23--27).-By
the interaction of inosite and phosphoric acid i n a
current of carbon dioxide, the author has prepared an acid, CGH1sO24PG,
which exhibits all the physical and chemical characters of the phosphoorganic acid obtained from the seeds of plants (compare Abstr., 1909,
i, 203). By treating its barium o r calcium salt with cupric and
sodium acetates, the salt CGH,0,,Cu,Ba2 or C,HG0,4Cu,lCn, is obtained,
whilst the calcio-magnesium salt agrees in chemical and physical
properties with the corresponding derivative of the phytin extracted
from rice bran (Zoc. cit.). On hydrolysis, the acid yields compounds poorer i n phosphorus, one of which, inosite-d~~~osphol.ic
acid,
C,H,,O,,P,, was fisolated as a white, deliquescent, vitreous mass, and
T.H. P.
its barzum salt, C,H,,O,,P,Ba,,
prepared and analysed.
Phosphoric Acid Esters 'of Carbohydrates. I. On Sucrosephosphoric Acid. CARLNEUBERG
and H. POLLAIC
(Biochem. Zeitsch,,
1910, 23, 515--517).-Sucrose
in water, freshly prepared calcium
oxide, phosphoryl chloride, and dry chloroform were kept together a t the
temperature of melting ice, and t h e following reaction took place :
2C,,H,,O,, + 2POC1, + 5Ca0 = 3CaC1, + H20+ 2C,2H1,0,,*0*P0,Ca.
The sucrose-phosphate of calcium was separated out and analysed ; it
is a fine, white powder, readily soluble i n water. The entrance of
phosphoric acid into the sucrose molecule completely abolishes i t s
W. D. N.
fermentability.
Lipoproteins and the meaning of Fatty Degeneration i n
Cells. V. Further Syntheses of Lipopeptides. VI. Further
Researches on the Cleavage of Lipopeptides. S. EONDIand
FRANZEISSLER(Bioclwrt. ZeitscJL, 1910, 23, 499-509, 510--513.
Compare Abstr., 1909, i, 458,459).-1n continuation of former work,
and by t h e use of the same methods, the following were prepared :
Butyryiglycine, m. p. 70'. Butyrylalanine, thin prisms, m. p. 88-93'
;
its ethyl ester has b. p. 135-145'/14
mm. Butyrylalanylglycine, thin
prisms, m. p. 171O. Palmitylalanylglycine, needles, m. p. 128-138',
not sharp. Lsurylalanylglycine, groups of needles, m. p. 141'.
isoValerylglycine, thin prisms, m. p. 87-90.
Laurylpeptoce, crystalline. Palmitylpeptone, a brownish-yellow powder. Witte's peptone
was used in the preparation of the two last-named substances. Unlike
proteins and nearly all non-aromatic amino-acids, they are all readily
soluble in alcohol. They are insoluble in light petroleum, and almost
so in ether,

i. 158

ABSTRACTS OF CHEMICAL PAPERS.

Butyrylglycine is not resolved by pepsin or trypsin, but is by a n

extract of autolysed kidney ; butyrylalanine is only slightly decomposed by a similar extract of liver. Trypsin has also no action on
butyrylalanylglycine or laurylalanylglycine. The latter substance,
however, is decomposed by autolysed kidney extract. No evidence of
reversible action mas found.
W. D. H.

A New M e t h o d of Forming isoCyanates [Carbimides] and

Hofmanns Thiocarbimide Reaction. 11. RICHARD
ANSCHUTZ
(Anncden, 1910, 371, 201-226.
Compare Abstr., 1908, i, 326)The behaviour of the mercuric and chloromercuric salts of eth ylthiolcarbnmic acid and isobutylthiolcarbamic acid when heated alone,
likewise the decomposition of mercuric and chloromercuric ethylditbiocsrbamates by boiling water and by heat alone, has been investigated
quantitatively, with the result that the conclusions published
previously (Zoc. c i t . ) have to be modified slightly.
Chloromercuric ethylthiolcarbamate when heated decomposes thus :
3NEIEt*CO*SHgCl -+ Hg,S,Cl, + COS + 2EtNCO + NH,EtCl ; in
this way it is possible to prepare alkylcarbimides without difficulty.
The corresponding ethyldithiocarbamate is decomposed by heat
analogously.
Mercuric ethylthiolcarbamate when heated alone decomposes into
red mercuric snlphide, carbonyl sulphide, and s-diethylcnrbsmide ; the
formation of hydrogen sulphide could not be detected, owing to the
readiness with which it interacts with ethylcarbimide, yielding
csarbonyl sulphide and s-diethylcarbamide. Mercuric ethyidithiocarbamate, when similarly treated, decomposes in two ways,
represented by the equations : [NHEt*CS*S],Hg --+ (1) HgS +
CS, + CS(NHEt), or (2) HgS + H,S + 2EtNCS ; the mercuric sulphide
obtained i n these reactions is black. The extent to which the
reaction represented by (2) takes place depends on the rate of heating,
for hydrogen sulphide and ethylthiocarbimide interact, yielding
carbon disulphicle and s-diethylcarbamide. The salt undergoes the
same change when boiled with water, but to a greater extent (about
50%) in the manner indicated by (2). I n the preparation of alkylcarbimides by. Hofmanns method, however, an excess of mercuric
chloride is employed ; this results in the formation of chloromercuric
ethyldithiocarbamate, which is decomposed by boiling water, thus :
NHF,t*CS*SHgCl=H g S + SCNEt + HC1.
The isobutyl salts undergo the same changes as the analogous ethyl
compounds.
Chloromercuric ethyldiihiocarbamatee is prepared by adding a n
aqueous solution of ethylammonium ethyldithiocarbamat e to a cold
solution of mercuric chloride in acetone; it crystallises in white
leaflets.
W. H. G.

Ethyl Oxalosuccinonitrile and D i e t h y l Dioxalosuccinonitrile.

WILHELH
WISLICENUS
and HEINRICH
ELVERT
(Beg-.,1910,43, 228-234.
Compare Abstr., 1908, i, 965).--Ethyl
oxalosuccinonitrile has
m. p. 112-113, not 102-103 as previously stated. A better yield
i s obtained i f the method of preparation formerly given is modified

ORGANIC CHEMISTRY.

i. 159

so as to ensure the presence of an excess of succinonitrile throughout

the reaction. According to observations made by A. Hantzsch and
H. Ley, alcoholic solutions of the @-form fluoresce. H. Ley and
von Engelhardt find that 0-005N-alcoholic solutions of the a-form
also fluoresce, but the fluorescence disappears when a n excess of sodium
ethoxide is added, so that i t is due t o the presence of a small
proportion of the p-form.
By doubling the quantities of ethyl oxalate and potassium ethoxide
taken, and reversing the order of addition in the method formerly described for the preparation of ethyl oxalosuccinonitrile, the dipotassium
salt of diethyl d ~ o x a l o s u c c ~ n o n i ~may
r i ~ ebe obtained (compare Nichael,
Abstr., 1903, i, 736). The substance gives a deep reddish-brown
coloration with ferric chloride, and ammonia is evolved when it is
boiled with ammonium chloride. On acidifying its aqueous solution,
the monopotassium salt is precipitated. It forms small, lustrous
needles, m.p. above 140' (decomp.), and gives a red coloration with
ferric chloride. Copper acetate yields with both potassium salts and
with the free nitrile the same nzonocopper salt, in the form of small
green needles, which become brown at 170, and melt at 220-225".
By acidifying a n aqueous solution of the potassium salt, the enolic
form of diethyl dioxalosuccinonitrile may be obtained as a viscous,
brown oil, which, on shaking with water, yields a hydrate which
forms colourless needles, m. p. 52-533, gives a weak red coloration with
ferric chloride, and is probably the dihyldmte. It readily loses water,
forming the monohydrate, m. p. 102-104'.
This hydrate also gives a
weak red coloration with ferric chloride. The enolic form and its
hydrates change spontaneously into the ketonic form, which crystallises in yellow prisms, m. p. 123-124O (Michael, Zoc. cit.).
The
alcoholic solutions of this substance do not fluoresce. It is probably a
ketonic enol of the constitution :
C02Et*Co*CH(CN)*C(CN):C(OH)*C02Et.
R. V. S.

Carbon Subnitride, C,N,. CHARLESMOGREU

and J. CH. BONGRAND
(Compt. rend., 1910,150, 225-227).-This
substance has been obtained
by the elimination of 2H,O from acetylenedicarboxylamide,
NH,*CO*Ci C*CO*NH, ;
it may therefore be regarded as dicynnoacetylene, NC*CiG.CN. The
analysis of the compound presented difficulties, but it has been shown
t o contain less than 0.6% of hydrogen. Carbon subnitride occurs as
slender, colourless needles, m. p. 20*5--31, b. p. 76'/753 mm.,
Dt50*9703. The vapour is powerfully irritant, and has an odour
resembling t h a t of cyanogen ; at 130' i t is spontaneously inflammable
in air, burning with a fiame like that of cyanogen. The molecular
refractions for the D-sodium line and for the a-,p-, and y-hydrogen
lines have been determined : M, 21.641 ; M,-Ma 1.023. Refraction
and dispersion are considerably higher than the values calculated on
the assumption that the compound has the foregoing constitution
(compare Abstr., 1906, ii, l), probably through the contiguity of the
three triple linkings.
The vapour density between 5 6 O and 184' is in agreement with the
formula C,N,.
w. 0. w.

i. 160

ABSTRACTS OF CHEMICAL PAPERS.

Naphthene Formation. IV. Formation of Naphthene from

Olefines and from Artiflcial Lubricating Oil and the Synthesis
of the Latter. CARL EKGLER
and 0. ROUTALA
(Bw.,1910, 43,
388-397).-The
conversion of olefines into naphthenes does not, as a
rule, take place directly. Probably, in the first place, polymerisation
to polyolefines takes place, and these, on account of their content of
labile hydrogen atoms, yield, firstly, paraffins, and subsequently decompose into naphthenee, on the one hand, and lubricating oils, on t h e
other.
When the decomposition is carried out at lorn temperatures, for
example, with aluminium chloride at the ordinary temperature, or at
the boiling point of amylene, relatively little naphtheiie is formed
along with paraffins and lubricating oil ; at higher temperatures
relatively more naphthene is formed, and the lubricating oils in part
decompose, forming naphthene.
When amylene is heated in tubes under pressure, methane and
hydrogen are formed. By the action of aluminium chloride on
amylene in the cold, a n oil is formed containing more than 87% of
carbon, having the composition CZnHglt-6,
and agreeing i n composition
and properties with natural lubricating oil.
When heated for some time at 350, the lubricating oil gives rise to
a mixture of unsaturated and saturated hydrocarbons ; the lower
boiling fractions are in the main honiologues of methane, the higher
boiling fractions contain increasing proportions of naphthenes.
E. F. A.

Naphthene Formation. V. The Products of Heating

and B. HALMAI
(Ber.,
Cylinder Oil Under Pressure. CARLENGLER
1910, 43,397--405).-Large
quantities of a Baku cylinder oil were
heated from four to six hours under pressure a t 400-430'.
The
product (b. p. 25--250) was carefully fractionated, and the constituents
of the successive fractions identified. The earlier fractions contained
almost entirely paraffin hydrocarbons ; as the boiling point rose, the
proportion of naphthenes present increased. The highest boiling
fractions consisted of lubricating oils, which behaved in a similar
manner to the nctturd oils and those synthesised from amylene.

E. F. A.

Naphthene Formation. VI. Possible Formation of Hydrocarbons in Nature, and the Origin of the Optical Activity of
Petroleum. CARLENGLER
(Bey., 1910, 43,405-411.
Compare preceding abstracts).-In
nature, bituniinated animal and plant residues
break down into solid paraftins, olefines, and liquid paraffins. The effect
of heat and pressure, in conjunction with long periods of time, causes
the solid paraffins to break down into liquid paraEns and olefines. The
olefines condense to polyolefines ; this gives rise t o liquid paraffins, naphthenes, and lubricating oils; the last a t a still higher temperature
undergo further decomposition into liquid paraffins, naphthenes, and
lubricating oils with 1e.s hydrogen.
None of these changes is
reversible. They take place simultaneously, and no great heat is
required if the period of time be long enough. The petroleum

ORGANIC CHEMISTRY.

i. 161

which have been exposed to the highest temperature contain most

naphthenes and lubricating oils, although they may be younger in the
geological sense than oils which contain mostly paraffins and have
been exposed to lower temperatures.
The explanation given is in agreement with the fact that oils rich
in naphthenes are usually rich in lubricating oils and vice versa. The
higher boiling fractions of the heated natural cylinder oil (see previous
abstract) still preserve some optical activity, and it would appear t h a t
the optically active constituents of petroleum oppose great resistance
t o racemisation by heat. Inasmuch as the heat in the natural process
is probably less than that used experimentally, the fact that the
natural petroleums are optically active is not in opposition to the
combiiied heat and pressure theory of their formation.
E. F. A.
R e l a t i o n between Colour and Constitution. IWAN
OSTROMIS(Bey., 1910, 43, 197--198).-A
claim for priority. Werner's
observations on nitro-compounds and his deductions therefrom (this
VOI., i, 80) had been made by the author in a paper sent to, but not
c. s.
published by, the German Chemical Society.
SLENSKY

Hydrocarbons from C i n n a m y l Chloride, CHPh:CH*CH,Cl.

HANSRUPEand J. BURGIN(Bey., 1910, 43, 172--178).-Cinnamyl
chloride, prepared by the action of hydrogen chloride gas on cinnamyl
alcohol (compare Emde, Abstr., 1909, i, 708), is a mobile liquid, b. p.
116-1 1 7 O p min., solidifying to large, colourless needles, m. p. 8-9'.
Cinnamyl bromide is obtained on heating cinnamyl alcohol with
phosphorus tribromide in benzene solution in colourless needles,
m. p. 30, b. p. 130/10 mm.
Cinnamyl chloride reacts with magnesium in ethereal solution ; the
product when decomposed with water yields a mixture of two hydrocarbons.
u[- Uiphenyl- Aaa-hexadiene, C H P h :CH*CH, CH,*CH:CHPh, forms
thin, irregular, colourless, lustrous plates, m. p. 82", b. p. 211'/11 mm.,
which i n solution show a reddish-blue fluorescence. It yields a tetrabromide, separating in colourless, feathery needles, m. p. 194'.
as-DiphenyZ-Aa-hexene, CHEtPh-CH,*CH:CHPh, is a colourless,
1.588; the hydromobile fluid, b. p. 190/11 mm., D20 0.9915, ':21
bromide is a dark viscid oil. The constitution is indicated by the fact
that, on oxidstion with potassium permanganate, benzoic acid and
phenylsuccinic acid are formed.
y-Chloro-a-phenylpropanecould not be prepared. y-Brornou-phenytpropune is obtained by the action of phosphorus tribromide on hydrocinnamyl alcohol; the colourless liquid has b. p. 109'/11 m m . The
bromide interacts with magnesium, forming propylbenzene and
diphenylhexane.
E. F. A.
Mobility of the Hydrogen Atoms of the M e t h y l e n e
Group in Compounds of the General Formulae
R-SO,. CH 2* CN, R=SO,*CH,=CO-NH,, R-SO,*CH,=CO,Et.
JULIUS
TROGER
and E. Lux (Arch. Pharrn., 1909,247,618--649).-The

i. 162

ABSTRACTS OF CHEMICAL PAPERS.

close analogy between P-sulphonecarboxylic acids and P-ketonic acids,

studied by Rossing (Abstr., 1890, 781) and Engelhardt (J.p r . Chew.,
1889, [ii], 40,540) and further illustrated by Michael and Comey by the
preparation of the sodium arid alkyl derivatives of the former (Abstr.,
1884, 319 ; 1885,906 ; 1890, 781), suggests t h a t the groups RSO, and
C0,Et exert the same influence as the groups RCO and C0,Et on the
neighbouring methylene group. The mobility: of the rnethylene
hydrogen atoms in arylsulphoneacetonitriles has already been shown
t o some extent by Troger and Hill0 (Abstr., 1905, i, 336), whilst t h e
similar behaviour of such nitriles and phenylacetonitrile with amyl
nitrite and sodium ethoxide and with aldehydes and sodium hydroxide
has been manifested by Tiiiger and Prochnow (Abstr., 1908, i , 798).
The present paper deals with the influence on the rnethylene hydrogen
atoms of compounds RSO,*CH,X exerted by different groups X (where
X = CO,R, CO*NM,, or CN), the case of arylsulphonated ncetnniides
being of special interest, since Troger and Lindner (Abstr., 190S, i,
633) have shown that the methylene hydrogen atoms of the corresponding arylsulphonated thioacetamides are not replaceable by alkali
metals or alkyl groups. The results of experiments on arylsulphoriated
acetonitriles, amides, and esters with alkalis, alkyl halides, aldehydes,
a n d amyl nitrite and sodium ethoxide show that in these compounds
the group CO*NH, does not act like CN, and exerts an influence similar
to, but weaker than, t h a t of the group C0,Et. For example, with
alkalis, arylsulphonated acetic acids yield carbon dioxide and sulphones ;
their esters yield disodinm deriratives ; arylsulphonated ace tarnidee are
insoluble i n sodium hydroxide, and arplsulphonated acetonitriles,
although soluble in dilute sodium hydroxide, are not hydrolysed even
by boiling, this only being effected by concentrated hydrochloric acid
under pressure. The action of alkali and alkyl halides on
RSO,*CH,*CO,Et
leads, as is known, to t h e formation of mono- and di-alkyl derivatives,
on RS0,*CH2*CXonly to the production of dialkyl derivatives, and on
RSO,*CH,-CO*NEI, results i n simple hydrolysis by the alkali.
Amy1 nitrite and sodium ethoxide simply hydrolyse arylsulphonated
acetic esters, but react smoothly with the amides and nitriles t o form
isoni troso-compounds by replacement of the methylene hydrogen atoms.
The compounds obtained from the nitriles have the formula
RSO,*C( :NOH)*CN,
and the following oximes and their derivatives are described; the
aodium and silver salts are yellow powders, and the lead salts yellomishwhite powders.

P11

R.

...............

p.
-

In.

y-C,H4Me ...... p-C,H,Cl ...... 147"

p-C, H4Br ...... p-C,H,I ......... 171
OMe'C,H ,...... 152
OEt'C,H, ...... 147

Hethyl
ether,
ni. p
57"
99

Benzyl
ether,
m. p.

115
125

SO

7:"

90

125

98
129

94

102

87

97

Benzoyl
derivatives,
in. p;,
153

Acetyl
derivatives,
ni. p.
91"

162
171
175

166

126
149

The following compounds, RS0,*C(:NOH)*CO*NH2,

are obtained in

ORGANIC CHEMISTRY,

i. 163

a similar way, but less readily from arylsulphonated acetamides ; the

figures are m. p.,s : R = P h , 153' (decomp.) ; R=p-C,H,Cl, 155O
(decomp.) ; R=p-C,H:,Br, 152' (decomp.) ; R =p-CGH,I, 178'
(decomp.); the sodium, silver, and lead salts have been prepared.
Troger and Prochnow (Zoc. cit.) have shown t h a t arylsulphonated
acetonitriles, like phenylacetonitrile, readily condense with certain
aromatic aldehydes in the presence of a little sodium hydroxide.
Arylsulphonated acetamides or acetic esters do not condense with
aldehydes as a rule, but from salicylaldehyde t h e same compounds,

Rs02a~-co>0, are obtained by loss of water and ammonia and

CH-C, H,
water and ethyl alcohol respectively. Of such CompoundP, the
following are mentioned : H, = Ph, 219';
R =p-C,H,Cl, 243' ;
R =p-CGH4Br,244' ; R =p-CGH41,248'.
The bromination of arylsulphonated acetic acids, esters, and amides
doe3 not proceed smoothly, but the nitriles yield compounds,
RSO,*CBr,-CN,
which are also obtained by the action of bromine on the sodium salts
of t h e corresponding oximes : R = Ph, 1233 ; R =p-U6H4Cl, 126' ;
R =pC,H,Br, 129' ; R =p-C,H,I, 132'.
c. s.

Aniline Antimony1 Tartrate. PAULYVON(Contpt. rend., 19 1 0,

150, 283-285).-Clarke's
salt, C4~50,(SbO)*C,H,N (Abstr., 1882,
1051), separates with 1 mol. H,O when allowed to crystallise from an
aqueous solution at 15" ; the crystals deposited at 35' are anhydrous.
The hydrated salt forms stellate clusters of long prisms, which become
opaque on exposure, losing water of crys tallisation.
I n 2-5% aqueous solution: the anhydrous salt has {a]; 121.28O,
D1*2.112 ; one gram of the substance is soluble i n 6-36grams of water
at 15'. The hydrate has [a]: 115.61', DZ01.569.
The solubilities in water and alcohol at different temperatures are
given, and also crystallographic details of t h e anhydrous-salt.

w. 0.w.

Complex Compounds of Aluminium Bromide with Organic

Compounds. IWAN
A. KABLUKOFF
and AL. SACHANOFF
(J.12uss.
Phys. Chem. Soc., 1909, 41, 1755-1'762.
Compare Menschutkin,
Abstr., 1909, i, 897, 900).-Investigation of the melting-point curves
of mixtures of aluminium bromide with benzene, toluene, xylene,
naphthalene, dibromomethane, bromobenzene, and p-dibromobenzene
iidicates either a slight tendency of these organic compounds t o give
double compounds with aluminium bromide, or the extreme instability
of such complex compounds. It seems, indeed, t h a t for stable
compounds to be formed with aluminium bromide, the presence of
oxygen or nitrogen i n the organic component is a necessary condition.
With aniline, four compounds are formed by aluminium bromide :
A12BrG,2NH,Ph,m. p. 90' ; A1,BrG,3NH,Yh,a.p. 114' ;
A12Br,,4NH,Ph,
m p. 105'; Al,Br,,8NH2Ph, m. p. 122'.
These compounds dissolve
in benzene or ether, and are decomposed by water, giving aluminium.
hydroxide and aniline hydrobromide.

i. 164

ABSTRACTS OF CHEMICAL PAPERS.

p-Bromoaniline gives two compounds : A12Br6,2C,H,Br*NH,, m. p.

Diphenylamine gives the
compound Aj2Br6,2NHPh,, m. p. somewhat above 200' ; dimethylaniline, A12Br,,2NMe,'h, m. p. 95' ; methylaniline,
Al2Br6,2NHMePh,
m. p. 7s"; nitrobenzene, A1,Br6,2Ph-NO,, m. p. 8 4 O ; pyridine,
A12Br6,4C5NH,, m. p. about 170" (decomp.) ; benzonitrile, the three
compounds : A12Br,,2Ph*CN, m. p. 140-150' ; A1,Br6,3Ph*CN, II;. p.
about 140, and A12Br6,4Ph*CN,m. p. about 150".
Of the oxygenated compounds, acids, alcohols, aldehydes, and
ketones form double compounds with aluminium bromide (compare
Walker and Spencer, Trans., 1904, 85, 1106). Further, esters of
benzoic acid give compounds of the formula A12Br6,2Ph*C02R,that
formed by methyl benzoate having m. p. 100". Esters of f a t t y acids
react energeticslly with aluminium bromide, hydrogen bromide being
evolved.
The double compounds formed by aluminium bromide with organic
nitrogen compounds are more stable than those containing organic
oxygen compounds. The existence of complex compounds containing
a n odd number of molecules of a n organic compound leads to the
conclusion that the aluminium bromide present exists in the form of a
doubled molecule, A12Br,.
T. H, P.

140", and A12Br,,5C,H,Br*NH2, m. p. 125'.

Preparation of Sodium Arylimides. DEUTSCHE

GOLD- &
SILBER-SCHEIDE-ANSTALT
(D.R.-P. 2 15339).--The replacement of a n
aminic hydrogen atom by sodium in aniline has been shown to occur
only after prolonged heating at a high temperature.
It is now found t h a t the reaction takes place much more readily i n
the presence of a catalytic agent, such as copper, nickel, cobalt, o r any
other heavy metal, its oxide, or salt.
Under these conditions, sodium reacts with aniline a t 140"; the
reaction also takes place with o-toluidine or methylaniline ; t h e
products are hygroscopic, fairly-stable substances, but are decomposed
by water into sodium hydroxide and original base.
F. M. G. &I.
Preparation of Cerium Phenoxides. CBEXISCHEFABRIK
AUF
AKTIEN VORM. B. SCHERING
(D.R.-P. 2147S2).-The
compounds
formed by the interaction of cerium salts with phenolic compounds
have similar disinfectant properties to the bismuth phenoxides, but
are less toxic and irritating than the phenols themselves.
Cerium phenoxide, prepnred from cerium nitrate, phenol, and sodium
hydroxide, is pale brown, odourless, and insoluble in water ; it contains
317; cerium.
Cerium o-methoxyphenoxide analogoiisly prepared is pink, insoluble
in water, but soluble in alcohol, chloroform, or ether.
Cerium /3-nuphthoxide has similar properties, and contains 30%
of cerium.
F. 11.G. 1T.
Behaviour of Pheuyl Sulphide towards Hydrogen Peroxide.

OSCARHINSBERG
(Bev.,l9 10,43,2S9--290).-When

a solution of phenyl
sulphide in glacial acetic acid is treated with the equivalent qnantit,y

i. 165

ORGANIC CHEMISTRY.

of hydrogen peroxide at the ordinary temperature, phenyl sulphoxide

is formed (compare Abstr., 1908, i, 875). If, however, a n excess (more
than 2' gram-molecules) of hydrogen peroxide is used, and the mixture
kept at the room temperature, crystals of phenyleulphone begin to form
after a few days. The quantity of sulphone is increased by precipitation with water. Phenylsulphoxide could not be detected in t h e
reaction mixture.
If acetone is used as the solvent (compare Smiles and Gazdar, Trans.,
1908, 93, 1833) there is no action between phenyl sulphide and
hydrogen peroxide at the ordinary temperature. Reaction only takes
place after heating for a n hour in a sealed tube a t 80--100", and even
i n the presence of excess of hydrogen peroxide, only phenyl sulphoxide
is formed.
It is assumed t h a t when glacial acetic acid is used as the solvent,
it takes part in the reaction, owing to the formation of peracetic acid,
CH,*CO *O OH.
T. S. P.

p-Tolyl Trisulphide. BRORHOLMBERG

(Be?., 1910, 43, 226-227).
-The author has shown previously (Abstr., 1908, i, 308) that the
mercaptans and thionyl chloride interact, with the formation OF
disulphide, trisulphide, water, and hydrogen chloride. H e now finds
that thionylaniline also reacts with mercaptans ; with ethyl mercaptan,
thioglycollic acid, and ethyl thioglycollate, the reaction is so violent
t h a t the reagents must be diluted with ether or carbon tetrachloride.
It is, however, very difficult to isolate pure products from the reaction
mixture.
When p-tolyl mercaptsn is used, the trisulphide is readily isolated.
The mixture of the mercaptan and thionylaniline was heated on the
water-bath. After cooling and remaining for a few days, a solid
separated, which had m. p. 81--82O, and proved to bep-tolgl trisulphide.
It forms small plates, thin prisms, or needles, and is pale yellow. The
crude solid was contaminated with a yellow oil, which was a mixture
of aniline, p-tolyl disulphide, and aniline sulphate, the latter compouud
resulting from the hydrolysis of some of the thionylaniline by water
formed in the reaction with the mercaptan :

4RSH + C,H,N:SO

= R,S,

+ R,S, + H20+ C,H,*NH2.

The following summary shows t h a t the melting points of the thio-diacetic acids and of t h e p-tolyl sulphides show a regularity similar to
t h a t observed in many homologous series of carbon compounds.
However, the member with an uneven number of sulphur atoms has
a higher melting point than the next member with an even number.
S(CH2*C0,H), .................
S,(CH2*C0,H)2.................
S,(CH2T!0,H), ..................
S,(CH;CO,H), ..................

129"

109
124
113

p-(C,H,Me),S
p-(C,H,Me),S,
p-(C,H,Rle)2S,
p-(C,H,Me),S4

..................... 57"
.................... 46
.....................
82
.....................
75
T. S. P.

Phenanthrene Series, XXVI. Conversion of 9-Chloro-10h y d r o x y p h e n a n t h r e n e into other Phenanthrene Derivatives.

JULIUS
SCHMIDT
and HERNANN
LUMPP
(Ber., 1910, 43. 423-438).-9-Chloro-10-hydroxyphenauthrene(Abstr., 1909, i, 35 j can be used for
VOL. XCVIIX.

i.

i. 166

ABSTRACTS OF CHEMICAL PAPERS.

t h e preparation of 3-nitrophe~anthraquinone(Zoc. cit.), of 9 : 1O-chloro3-bromohydroxyphenanthrene, and other phenanthrene derivatives.

9 (1O)-ChZoro-3-bromo-lO( 9)-hydrox?llp~~en~nlhrene,
C,,H80Cl13r, prepared by the action of a carbon disulphide solution of bromine on
9-chloro-lO-hydroxyphenanthrene,
forms colourless prisms, m. p. 142',
and dissolves in aqueous solutions of alkalis. I t s acetyl derivative,
C',,H,,O,ClBr, has m. p. 158-159',
and the bmxoyl derivative,
c 2 p & C l Br,
which crystallises in yellow prisms, m. p. 179-1 80'.
When reduced with zinc dust and glacial acetic acid, t h e bromoderivative yields 3-bromo-9(lO)-hydroxyphenanthrene,C,,K,OEr, which
could not be crystallised on account of the readiness with which i t
dissolves in most solvents. I t s acetyl derivative, ClGH1102Br,crystallises in pale yellow prisms, m. p. 135'. The position of the bromine
atom in the chlorobromohydroxyphenanthrene follows from the readiness with which it can be oxidised by chromic acid to S-bromophenanthraquinone (Schmidt and Ladner, Ber., 1905, 37, 3571), which
appears to exist in yellow and reddish-brown chromo-isomeriiles.
The dioxime, C1,H902N2Br,prepared by Schmidt. and Soll's method
(Abstr., 1907, i, 630), forms green, crystallifie aggregates, m. p. 212'
(decomp.). The monosemicarbaxone, Cl,Hl,02N,Br, forms yellow
crystals, m. p. 242' (decomp.), and the mono;D?LenyllL~draxone,

C&,,ON,Br,,

has ni. p. 17'7'.

The quinone can be reduced to the quinol by means of phenylhydrazine, but i t is difficult to isolate tho free dihydroxy-compound. Its
acetyl derivative, 3-bromo-9 : 10-diacetoxyphenantlwene, ClSHl3O4Br1
crystallises in colourless needles, m. p. 177-1 78'.
3 : 9( lO)-Dihydroxyphenanlhrene, C,,H,(OH),, formed when the
3-bromo-9(10)-hydroxy-compound is fused at 340' with potassium
hydroxide, crystallises in colourless prisms, m. p. 175". The yield is
small,
Fuming nitric acid converts the bromophenanthraquinone into a
dinitro-derivative, C,,H,O,N?Br,, which crystallises in pale yellow,
slender needles, m. p. 298'.
The monoxime, C,,H,O,N,Br, forms green
prisms, m. p. 196' (decomp.) ; the semicn~baxone,C15H,06N,Br, forms
yellowish-brown prisms, m. p. 272'.
The dinitro-quinone condenses with a n alcoholic solution of o-phenylenediamine hydrochloride, yielding 3-broinodiszitropl~enantl~rapJ~enccxine,
C,,H,O,N,Br, as a reddish-white powder, and, when heated on the
water-bath with concentrated aqueous ammonia, the quinone yields
3-brmonitroaminophenant?~rccpuinone,NO,*C1,H,BrO2*NH2, as a dark
brown substance, m. p. 280-282' (decomp.). The diacetyl derivative,
C18H110,~,Br,
forms a n ochre-yellow powder, m. p. 260' (decornp.).
Reduction of the 3-bromodinitrophenanthraquinone with tin and
concentrated hydrochloric acid leads to the formation of 3-chlorodiamilzophenanthraquino~,which can be readily oxidised by atmospheric
~uinoize,
The
oxygen to 3 - ~ h l o r o d i a r n i n o p ~ e i ~ ~ ~ n ~ ~ r aCl4H,ClO2(NH2),.
base can be diazotised readily, and the diazo-solution forms azo-dyes
with phenols. The dioxime, C14H,102N4CI,forms a deep bluish-black
powder, m, p. 2 6 4 O (decomp.). When the diamino compound is diazo-

ORGANIC CIIEMISTRY.

i. 167

t ised and tho solution boiled, 3-chZ o r o d i ~ y d r o ~ y ~ T L e a ~ ~ t ~ r a ~ ~

C,,H,ClO,(OH),, is obtained as a dark red powder, which is not a
substantive dye. The acetyl derivative, C,,H,,O,Cl, forms brownish-red
crystals, m. p. 245'.
J. J. S.

Preparation of Carbonateguaiacol-5-sulphonicAcid and its

Salts. F. HOFFMANN,
LA ROCHE& Co. (D.R.-P. 215050. Compare
Abstr., 1909, i, 780).-The
preparation of carbonatoguaiacol-5sulphonic acid and its salts by the action of concentrated sulphuric
acid on guaiacol carbonate has been described previously. The free
acid forms colourless to dark red, hygroscopic crystals ;its cold aqueous
solution gives no colour with ferric chloride, but, on heating, carbon
dioxide is evolved.
Potitssiutn carbonatoguaiacoZ-5-s~~p~onnte
crgstallises in needles, has
a neutral reaction, gives no colour ,with ferric chloride, but by prolonged boiling of its aqueous solution is decomposed into potassium
guaiacol-5-sulphonate with evolution of carbon dioxide.
F. M. G. RE.
Hydroxyphenylalkylamines and DihydroxyphenyldkylamineS. CARL MANNICHand w. JAcossoHN (Be?.., 1910, 43,
1 89--197.
Compare Rosenmund, this vol., i, 106 ; Barger, Trans. ,
1909, 95, 1123, 21 93).-Homologues of p-hydroxyphenylamine have
been obtained by reducing aldoximes or ketoximes t o bases of the type
OMe*C,H;CH,-CHR*NH,
or C,H,(OMe),*CH,=CHR-NH,,
and
converting these by heating with hydriodic acid into the corresponding
phenolic amines. The ketones selected were pmethoxybenzyl methyl
ketone, 3 : 4methylenedioxybenzyl methyl ketone, and 3 : 4-dimethoxybenzyl methyl ketone ; the aldehydes were p-methoxyphenylacetaldehyde and 3 : 4-dimethoxyphenylacetaldehyde.
To obtain p-methoxybenzyl methyl ketone, b. p. 136-140/12 mm.,
anethole was converted into the dibromide, and this into the bromohydrin, OMe*C,H4;CE-I(OH)*CHMeBr,which on heating with alcoholic
potassium hydroxide gave anetholoxide ; this, on heating at 220",
undergoes rearrangement to the ketone, OMe*C,H,*CH,*COMe. The
oxime, on reduction with sodium amalgam in acetic acid solution,
forms p-methoxyphenyZisopropyZamine, OMe*C,H,*CW,*CHMe=NH,,. a
colourless, strongly alkaline oil, b. p. 15S0/25 mm. j the hydroclJorzde
forms large, colourless crystals, m. p. 210'.
p-HydroxyphenylisopropyZamine crystallises in colourless rosettes,
m. p. 125-126';
the ltydriodide has m. p. 155'.
isoEugenoZinethyl ether bromohydrin, C6H,(OMe),*CH( 0 H) * CH MeBr,
has ru. p. 75". It yields the oxide already described by Fourneau and
Tiffenenu (Abstr., 1905, i, 591), which readily undergoes rearrangement to 3 : 4-dimethoxybenzyl methyl ketone, b. p. 198O/20 mm.
3 : 4-Dimetl~oxyphenyZisopropyZarnineis a n almost colourless oil,
b. p. 166-11;S0/20 mm. ; the hydrochloride has m. p. 144". 3 : 4-Dih y d r o ~ ~ p h eZisoprop~Za~~ne,
ny
C,H,( OH),* CH,*CHMw NH,, yields a
hydyochlmide, m. p. 190-192'.
TL2

i. 168

ABSTRACTS OF CHEMICAL PAPERS.

3 : 4-MethyZenedioxyphenylisop~*opyZamins
is a colourless oil, m. p.
157"/22 mm. ; the hydrochloride has m. p. 18O-18lo.
Homoanisaldehyde, OMe*C,H,*CH,*CHO, is conveniently prepared by oxidation of p-methoxyetyrene with mercury oxide and
iodine ; the oxime forms prisms, m. p, 120' (compare Rosenmund, this
vol., i, 106).
The oxime of homoveratraldehyde crystallises in prisms, m. p.
$0-9lo;
the oxime of veratraldehyde has m. p. 83".
On reduction, the oxime yields 3 : 4-dirnethoxyphenylethyZamine, a faintly
yellow-coloured oil, b. p. 18t3'/15 mm.; the hydrochloride has m. p.
154-1 55".
3 : 4-Dihydrox,yphen ylethyhmina, C,H,(OH),* CH,=CH,*NH,, forms
a crystalline hydrochloride, decomp. 220' ; it shows a green coloration
with ferric chloride.
E. F. A.

Quinocarbonium Perchlorates (11) and the Solvent Action

of C h l o r i n a t e d Ethanes. KARLA. HOFMANN,
HEINZ
KIRMREUTHER,
and A. THAL(Ber., 1910, 43, 183-188.
Compare this vol., i, 3).The triphenylcarbinyl perchlorates crystallise so well that pure
preparations are readily obtained from impure carbinols. I n accordance with their intense colour, they are easily ionised, so t h a t in
solvents such as tetrachloroethane, which is unable t o dissociate
triphenylmethyl chloride, they still conduct the electric current.
Aurin perchlomte forms doubly refractive, four-sided prisms, which
in direct light are orange-red with a light blue reflex. p-Trianisylcarbinol perchlorate (compare Gomberg and Cone, this vol., i, 55)
crystallises in cinnabar-red, fiat needles. It is relatively stable towards
water.
Triphenylcarbinyl perchlorate dissolves with a reddish-yellow
coloration in tetrachloroethane, and tri-p-anisylcarbinol perchlorate
with a n intense orange coloration. Both solutions conduct electricity,
likewise those of the perchlorates in ethylene chloride.
The solubility of the perchlorates in a number of solvents has been
compared by the intensity of the colour produced in the saturated
solution. The solvents take the following order, t h e more highly
coloured coming first : ethylene chloride, tetrachloroethane, chloroform, dichloroethylene, pentachloroethane, trichloroethylene, perchloroethylene, carbon tetrachloride. The last two or three solvents
only become coloured when boiled with the perchlorate. Mercuric
chloride dissolves in these solvents in precisely t h e same order, the
solubility being greatest in ethylene chloride and almost nothing in
carbon tetrachloride. This confirms the view t h a t the perchlorates
are of the nature of metallic salts.
The solvents dissolve sulphur in a n altogether different order,
ethylene chloride being the least, perchloroethylene t h e most, effective
solvent.
E. F. A.

Action of a-Bromonaphthalene and M a g n e s i u m on Certain

Carbonyl Compounds. E. SCHURAKOVSKY
(J. Rwse. Phys. Chem.
Soc., 1909, 41, 1687--1694).-The
interaction of a-bromonaphthalene,
magnesium, and acetone yields the compound MgBr*O*CMe,*C,,H7,

ORGANIC CHEMISTRY.

i. 169

which is decomposed by water, giving a-naphthyldimethylcarbinol

(compare Grignard, Abstr., 1901, i, 393). When heated with
anhydrous oxalic acid, this alcohol yields P-naphthylpropylene
(Crignard, Zoc. cit.), b. p. 251-251.5'/744
mm., DF 1.0078,
d51.60684 ; the molecular refraction, calculated according to the
Lorenz and Lorpntz formula, is 57.554, which, as is often the case
with naphthalene derivatives, diff ers considerably from the calculated
value, 55.38'7.
p- T o Z y Z - a - n a p ~ t l y Z ? n ~ t ~ ~ ~ ZC,H,Me*
c a r ~ ~ ~CMe(
Z , C,
OH, prepared
from a-bromonaphthalene, magnesium, and tolyl methyl ketone, was
obtained as a dark viscous, impure mass. When heated with
anhydrous oxalic acid, this alcohol loses water, giving as-a-naphthyl-ptolylethylene, C6H,Me*C(C,o~7):CH,, which is a viscous, faintly
yellow liquid, b. p. 224--226O/20 mm., DZl5 1.0693, and combines
with ZBr per mol.
Anisy Z-a-naphth ylcarbinol, OMe*C,H,*CH( CloH7)*OH, prepared
from a-bromonapht halene, magnesium, and anisaldehyde, crystallises
in small needles or rhombic prisms, m. p. S7".
a-.NaphthylpropenyZcar6inoZ, CHMe:CH*CH(C,,K,)*OH, prepared
by the interaction of a-bromonaphthalene, magnesium, and crotonaldehyde, is a faintly yellow, viscous liquid, b. p. 204-210/22 mm.
T.H. P.

Preparation of Nitriles. E. EMMET

REID(Anzer. Chem. J . , 1910,
43, 162--1Sl).-It
was shown by Letts (Abstr., 1572, 1020) that
nitriles can be prepared by the action of potassium thiocyanate on
organic acids.
Kriiss (Abstr., 1884, 1314) found in the case of
benzonitrile that a better yield could be obtained with lead thiocyanate than with the potassium salt, the reaction being represented
by the equation :
2C,H,*C@,H+ Pb(CNS), = ZC,H,.CN + PbS + H2S+ 2C0,.
I n attempting to prepare benzonitrile by Kruss' method, the yield
obtained amounted to only 36% of the calculated, and it was observed
that only a very small quantity of hydrogen sulphide was evolved.
It was therefore considered likely that the hydrogen sulphide might
have entered into the reaction and led to the formation of complex
products, In order to avoid the formation of hydrogen sulphide, R mixture of lead benzoate and lead thiocyanate mas heated, and it was found
that, in these circumstances, a much better yield of benzonitrile was
obtained. Experiments have been made to ascertain the effect of heating
lead, sodium, zinc, and barium benzoates with potassium cyanate, lead
cyanate, potassium t hiocyanate, lead thiocyanate, barium thiocyanate,
lead ferrocyanide, lead cyanide and sulphur, lead ferrocyanide and
sulphur, zinc ferrocyanide and sulphur, potassium ferrocyanide and
sulphur, and silver cyanide and sulphur. I n each case a considerable
quantity of benzonitrile was obtained. The results of these experiments are tabulated.
The best method of preparing benzonitrile in the laboratory is to
distil a mixture of dry zinc benzoate and dry lead thiocyanate, a yield
of 79-9 1%being thus obtained.
A mixture of equivalent quantities
of lead ferrocyanide and sulphur may be used instead of the thiocyanate

i. 170

ABSTRACTS OF CHEMICAL PAPERS.

and, in this case, a yield of about 74% is produced.

The formation of
the benzonitrile takes place as follows :
Zn(C02*C6H,),+ Pb(CNS), = P b S + ZnS + 2C0, + 2C,H,*CN.
On applying this method to other acids, it was found that t h e
nitriles of the three aminobenzoic acids, p nitrobenzoic acid, salicylic
acid, and phthalic acid, could not be obtained in this way, but that when
lead rn- or p-bromobenzoate was distilled with lead thiocyanate, a
satisfactory yield of the bromobenzoni trile was produced in each case.
E. G.

Action of Alcoholic Hydrogen Chloride on m-Methylnitrosoa m i n o b e n z o i c Acid. JOSEF

HOUBEN
and WALTER
BRASSERT
(Ber.,
1910,43,206-212.
Compare Abstr., 1909, i, 92I).--m-Aminobenzoic
acid in glacial acetic acid is treated with methyl sulphate. After
one hour's heating and keeping for twelve hours, the crystals of
m-aminobenzoic acid sulphate are removed, and the filtrate is treated
with sodium nitrite a t 0', whereby m-methyl.lzitrosoaminobenxo~c acid,
NO*NMe*C,H,*CO,H, m. p. 179-180'
(bath previously at 16c1), is
obtained, which separates, slightly impure, from water in blood-red
leaflets, and is converted after two weeks by alcoholic hydrogen
chloride into ethyl m-metlzylaminobennxoate Iydrochloride, m. p. 137'
(corr.), which is converted into ethyl m-?nsth?llnitrosoamin~b~n~o~te,
m.p.
3 2 O , by nitrous acid a t 0". After twenty-four hours, m-methylnitrosoaminobenzoic acid and alcoholic hydrogen chloride yield m-methylanzinobenxoic acid hydrocMoride, CO,H*C,H,*NHMe,HCl, m. p. 244',
which is converted by N-sodium hydroxide into m-methylaminobenzoic
acid, m. p. 127' (corr.).
c. s.
New Drugs. V. ALFRED
EINHORN
(Annulen, 1910,371, 125-131.
Compare Abstr., 1900, i, 439, 493; 1903, i, 257 ; 1908, i, 312).-Mainly a resume of the work which led to the preparation of novocaine
(o-diethylaminoethyl p-aminobenzonte hydrochloride : corn pare
Farbwerke vorm. Meister, Lucius and Briining, Abstr., 1907, i, 923).
As far as can be ascertained, all soluble aromatic esters, with the
apparent exception of a-cocaine (compare Willstatter, Abstr., 1896, i,
707), are capable of producing local anaesthesia to a greater or lecs
degree. Generally speaking, the anaesthetic action is destroyed by the
introduction of a carboxyl OF sulphoxyl group into the molecule ;
other substituents, such as halogen, hydroxyl, alkoxyl, nitro, amino,
etc., either increase or diminish, but never destroy completely, the
activity of an aromatic ester.
w. Q.I.
Diethylaminoethyl and Piperidinoethyl p-Aminobenzoates.
ALFRED EINHORN
and EMIL UHLFELDER
(Annulen, 1910, 371,
131-1 42).-An
account of the preparation of diethylaruiuocttiyl
p-aminobenzoate (novocaine), piperidinoethyl p-aminobeu zoa te, and
some derivatives of these esters, much of which has appeared already
(compare Farbwerke vorm. Meistcr, Lucius and Briining, Abstr., 1507,
i, 923 ; 1908, i, 638).
Diethylaminoethyl p-aminobenzoate cbrystallises with 2H,O in s m a l l
needles, m. p. 51' ; the anhydrous substance ciysiailises in plates,
m. p. 61" ; the following derivatives have been prepared : mercuri-

i. 171

ORff ANIC CHEMISTRY.

chloride, needles, m. p. 139'; hydriodide, small needles, m. p.

121-122' ; merczcei-iodide, C,,H,,O,N,,HI,HgI,, small, white needles,
m. p. 127' ; nitrate, needles, m. p. 100-101' ; argentonitrate, needles,
m. p. 107'; sulphate, prisms, m. p. 170'; chlorate,
C,,J32,O,N,,HClO,,
needles, m. p. 89O ; borate, C,, H,,O2N2,4B(OH),, small needles, m. p.
159-1 60' ; trichloroacetate, prisms, m. p. 89O ; thiocyanate, prisms,
m. p. 83'; phthnlate, prisms, m. p. 119'; ethochloride,

NH,*C6H4*C02*CH2*CH2*NEt,Cl,H,0,
prisms, sinters a t 135O, and is completely molten a t 180'; the anhydrous
ethochloride has m. p. 198' (decomp.) ; cccetyl derivative, a viscid oil,
the hydriodide of which, C,,H,,O,N,,HI,
crystallises i n small rosettes,
m. p. 146-147 ; the hydrochlorade of the benxoyl derivative,
C,0H240,N,,HC1,

forms small needles, m. p. 189' ; the p-nitrobenxoyl derivative crystallises in small needles, m. p. 129-130',
and when reduced yields the
corresponding p-aminobenxoyl derivative, small needles, m. p. 124",
the hydrochloride of which, C,,H2,0,N,,HCl, crystallises in needles,
m. p. 221O.
Piperidin.oethyE p-ucetylaminobenzoate, Cl6H22O3N2, crystallises in
needles, m. p. 86-87' ; tho hydrochloride has m. p. 228'; the ester is
converted by a hot alcoholic solution of hydrogen chloride into the
dihpdrochloride of piperidinoethyl p-aminobenzoate, m. p. 225O.

W. H. G.

Alkylaminoalkyl p-Aminobeneoates. ALFRED

ELNHORN,
KARL
CARL LADISCH,
and EMILUHLFELDER
(Annulen, 191 0, 371,
FIEDLER,
142-1 6 l).-The compounds described i n this paper were prepared
subsequently to novocaine, but not one of them is more suitable than
this substance for the purpose of producing local anaesthesia. They
are all obtained by the reduction of the corresponding p-nitrobenzoates,
which are prepared by the action of p-nitrobenzoyl chloride on the
requisite alkamine.
Dimethylaminoethyl p-nitrobenxoate,

NO,*C6H,*CO2*CH,*CH2=NMe2,
prepared by heating dimethylaminoethyl alcohol with p-nitrobenzoyl
chloride a t 130, crystallises in slender, matted needles, m. p. 58-59' ;
when reduced with tin and hydrochloric acid, it yields the corresponding amino-compound, C,,H,,O,N,,
crystallising in large prisms, m. p.
12 lo, the hydrochloride of which, C,H,,O,N,,HCl,
forms small, slender
needles, m. p. 185-186'.
Diisop~.op?llaminoetT~ylp-nitrobenxoate is an oil ; the hydrochloride,
C1,H,20,N,,HCl,
crystallises in small needles, m. p. 136.5' ; the
corresponding amino-compound, C15H2402N2,crystallises i n slender
needles, m. p. 4S0,and forms a hydrochloride, crystallising in prisms,
m. p. 195'.
Diisobutylumi~zoetr~lp -witrobenzoute is a n oil ; the hydrochloride,
C,7H,,04N,,HC'l, forms slender, felted needles, m. p. 160--161' ; the
amino-compound, C17H2,0,N2, siuall, slender needles, m. p. 84-85',
forms a hydrochloride, which crystallises i n prisms, m. p. 195 -196'.
Diisoamyluminoethyl p-nitrobenxoate is a n oil j the hgdrochloride,

i. 172

ABSTRACTS OF CHEMICAL PAPERS.

Cl,H,o04N2,HCl, crystallises in small needles, m. p. 123-124' ; t h e

ammo-compound, C,,H,,O,N,,
leaflets, m. p. 44-45O, forms a hydrochloride, crystallising in needles, m. p. 154'.
Diethylaminornethylmethylethylcarbinol, NEt,*CH,*CMeEt*OH, prepared by t h e action of diethylamine on t h e corresponding chloro-compound, is an oil, b. p. 71-73"/15.5
mm. ; t h e p-nitrobenzoate is a n
I,
pale yellow crystals,
oil, the hydriodide of which, C l , H ~ 4 0 4 N ~ , Hforms
m. p. 167'; t h e p-aminobenxoate is a pale yellow oil, t h e picrute of
which, C,,H,,O,N,,
is a pale yellow, crystalline powder, m. p. 121'.
Piperidznometl~ylmet?~yl~t~~ylcarbinol,
NC5Hlo*CH;CMeEt*OH, is a
colourless oil, b. p. 101-104/18 mm. ; t h e p-nitrobenzoate is a viscid,
yellowish-brown oil, t h e hydriodide of which, C17H,,04N,,HI, crystallises in yellow leaflets, m. p. 190'; t h e p-aminobenxoate is an oil,
crystalline salts of which could not be obtained.
Diethylaminomethylethylcarbinol has b. p. 197-200'
(compare
Paal and Weidenkaff, Abstr., 1906, i, 236) ; t h e p-nitrobenxoate is an
oil, t h e hydriodide of which, C17H2,04N,,HT, crystallises i n yellow
prisms, m. p. 154'; t h e hydrochloride of t h e oily p-aminobenxoate,
C17H2,0,N,,HCI, forms rhomboidal crystals, m. p. 166-1 6 7".
Tetraethyldiaminoisopropylp-nitrobenxoate,
N0,*C,H4*C0,*CH(CH,-NEt,),,
forms yellow crystals, m. p. 41' ; t h e dihydrochloride crystallises i n
slender, felted needles, m. p. 198' ; t h e p-aminobenxoate, Cl8.H3,O2N3,
crystallises i n colourless leaflets, m. p. 50' ; the dihydrochlorsde forms
faintly yellow, slender needles, m. p. 222'.
Dipiperidinoisopropyl p-nitrobenzoate,
N02*C,H,~C02*CH(CH2*NC,H,o).2r
is a n oil ; t h e dihydriodide crystallises in lemon-yellow, slender needles,
m. p. 232' ; t h e corresponding amino-compound, C20H,,0,N3, forms
colmrless prisms, m. p. 137*5', the dihydrochloride of which crystallises
i n slender needles, m. p. 261'.
The p-nitro benzoate of a-dieth ylaminopropane - P y - diol,

NEt,*CH,~CH(OH)*CH,*CO,-C,H,*NO,
or
N E t 2 * CH,*CH(CO,*C,H,*KO,)*CH,*OH,
is an oil ; t h e hydrochloride is a microscopic, crystalline powder, m. p.
152" ; t h e corresponding amino-ester is a n oil ; the di-p-nitrobenzoate,
C,,H,,O,N,,
forms small, yellow needles, m. p. 90-92';
the
da-p-aminobenzoate has m. p. 132' ; t h e hydrochloride, C,,Hq70,N,,HCI,
is a crystalline powder, m. p. 185'. The p-nitrobenzoate ot t h e corresponding piperidino-compound, C15H2,0,N2, forms leaflets, m. p. 60- 63';
t h e ILydrochZoride crystallises in white needles, m. p. 212'; the
p-aminobenxoate, C,,H,,O,N,,
crystallises in prisms, m. p. 91" ; the
hydrochloride forms white needles, m. p. 206O ; t h e di-p-nitrobenxoate,
C5NH,o*CH,*CH(C0,~C,H4*NOz)*CH2*C02~C6H4*NOz,
crystallises i n
pale, yellow prisms, m. p. 108' ; the d i - p aminobenxoate crystallises in
prisms, m. p. 127" ; the hg'drochloride, C2,H2'704N3,
HCI, forms small
needles, m. p. 210.5'.
W. 1. G.

Esters a n d A l k y l a m i n o - e s t e r s of 3 : 4 - D i a m i n o b e n z o i c
B a d . ALFREDEINHORN
and EWILUHLFELDER
(Annalen, 1910, 371,
162-179. Compare Eiuhorn, Abstr., 1908, i, 639).-The
compounds

ORGANIC CHEMISTRY.

i. 173

described in this paper were prepared with the object of obtaining

derivatives of alkyl 3 : 4-diaminobenzoates yielding salts with a neutral
reaction, which could consequently be employed as anesthetics. The
esters of 3 : 4-diaminobenzoic acid when boiled with organic acids
yield esters of 2-alkylbenziminazole-5-carboxylic
acid, and when treated
with acetyl chloride yield t h e corresponding dichloroacetyl derivatives ;
the latter substances interact with secondary bases, for example,
piperidine, yielding the dipiperidinoacetyl compounds.
Methyl 2-methy l benxirninaxole-5-curboxylate,
s(CO,Me)*CH: $!-N
CHCH:C*NH>CMe
crystallises in needles, m. p. 172'; the hydrochloride forms small
needles, m. p. 25'7'; the ethyl ester crystallises in needles, m. p. 180'.
MetluJ 2-ethylbenziminazole-5-carboxylate,C,,H,202N2, crystallises in
needles, m. p. 141'; the hydrochloride has m. p. 252'. The dibsnzoyl
derivative of methyl 3 :4-diaminobenzoate, C2,H1804N?, crystallises in
small, white needles, m. p. 231' ; the dichloroacetyl derivative,
CO,Me*C,H,( NH*CO*CH,CI),,
forms needles, m. p. 177" ; the dipiperidinoacetyl derivative,

CO,Me*C,H,(NH*CO*CH,*NC,Hlo),
has m. p. 108'.
Ethyl 3-nitro-4-chloroacetylarninobenzoute,
CllHliO,N,CI, crystallises
in small, yellow needles, m. p. 102'. Ethyl 3-nitro-4-piperidicfoacetyL
arninobenzoate crystallises in yellow needles, m. p. 70-71', and when
reduced with tin and hydrochloric acid below 35" yields t h e corresponding ccmino-compound, C,,H,,O,N,, small needles, m. p. 103', the
hydrochloride of which crystallises in leaflets, m. p. 204O, whilst at a
higher temperature it is converted into ethyl 2-pipericlinonzethylbenzirnina~ole-5-cnrboxylate,
C1,H2,O,N,, a n oil, the dihydrochloride of which
crystallises in needles, m. p 221'. The following compounds are
similarly prepared : ethyl 3~atro-4-diethylglycylaminobenzoate,
NEt,*CH2*CO*NH*C,H3(
NO,)-CO,Et,
yellow needles, m. p. 71" ; ethyl 3-amano-4-diethy?gZycyla~ni~zobenaoate,
small needles, m. p. 64' ; hydrochloi*ide, needles, m. p. 194' ; etlql 2d iethylaniinomet hyl!benziminazole- 5 -carboxylate, C ,H2,0,N3, pointed
needles, m. p. 67' ; hydrochloride, bmall needles, m. p. 173' ; dihydrocldoride, m. p. 199'.
Chloroethpl 3 : 4-diaminobenzoate, C,H,(NH2),*C0,*CH2*CH2Cl,is
obtained by acting on a mixture of 3 : 4-diaminobenzoic acid and
ethylene cblorohydrin with hydrogen chloride in the presence of a
small quantity of concentrated sulphuric acid ; it crystallises in
needles, m. p. 80, and, when heated with diethylamine under pressure
at 100- 1 Z O O , yields the corresponding diethylaminoethyl ester, a n oil,
the hydrochloride of which, C1,H,,O,N,,HC1, forms needles, m. p. 163' ;
the picrate crystallises in yellow needles, m. p. 189-190'.
The
diethylaminoethyl ester undergoes the following changes : (1) with
glyoxal, it yields diethylaminoethyl quinoxaline-6-carbox~late,
an oil,
the hydrochloride of which, Cl,H2,02N,,HC1, cry stallises i n needles,
m. p. 1 8 7 O ; (2) when treated with sodium nitrite and hydrochloric
acid, it yields diethylaminoethyl 3 : 4-aziminobenxoate hydrochloride,
Ci,H1,O2N,,HCl, small needles, m. p. 150-151' j (3) i t condenses

i. 174

ABSTRACTS OF CREMICAL PAPERS.

with p-dimethylaminobenzaldehyde,yielding a substccnce, which crystallises in yellow needles, m. p. 161', and with benealdehyde, yielding a n
oily substance, the hydrochloride of which crystallises in prisms,
m. p. 190'.
Piperidinoethyl3 :4-diarninobenxocctecrystallises in needles, m. p. 103' ;
when heated with glacial acetic acid, it yields pipericlinoethyl 2-methplbe~zximin~~oZe-5~cc~rboxyZ~te,
C1SK2202N3,
needles, m. p. 159-160, the
hydrochloride and dihydrochloride of which crystallise in needles,
m. p. 162-163" and 262' respectively.
Bietl~yZc~minoeth~~Z
3-nitro-4-dinacthylaminobenxoc~te,
prepared from
3-nitro-4-dimethylaminobenzoicacid and diethylaminoethanol, is a n
oil; the corresponding amino-compound, also a n oil, forms a hgdrochloyide, C,,H,,O,N,,HCl, which crystallises in needles, m. p. 164'.
Methyl 3 : 4-tet~~amethyldiarnirtobenzoate
dihydriodide, prepared by
heating methy 1 3-amino-4-dimet h y laminoben zoa t e with met hy 1 iodide
and methyl alcohol under pressure at loo', crystallises in needles,
m. p. 109-1 10' ; the dihydrobromide, C,,H1,0,N,,2HBr, crystallises in
needles, m. p. 205O ; the correspondiug diethyhninoethyl ester is a n
oil ; the hydrochloride, 'J'17H2,0,N,,crystallises in small, white needles,
m. p. 140-141.
W. H. G.

(Bey.,
Isomerism of Anils (Schiff's Bases). OTTOANSELMINO
1910, 43, 462-463.
Compare Manchot and Furlong, Abstr., 1909, i,
805 ; this vol., i, 33 ; Anselmino, Abstr., 1906, i, 13 ; 1907, i, 913 ;
Knoevenagel and Schrotter, Abstr., 1905, i, 64).-Polemical.
J. J. S.

Differences between Cinnamic Acid from Storax and

Synthetical Cinnamic Acid. C. E. RIIBER and V. MORITZ
GOLDSCHMIDT
(Ber., 19 10, 43, 453-462.
Compare E. Erlenmeyer,
jun., Abstr., 1907, i, 318 ; 1909, i, 156, 647, 648).-Although cinnamic
acid from storax differs so materially in habit from the Synthetical
acid, it is shown that the characteristic crystnllographic constants are
the same for the two acids. The chief differences are ( a ) the extremely
thin plates in which the synthetical acid crystallises ; ( b ) the absence of
definite faces in the crystals of the synthetical acid ; the plates as a
rule have a crinkled edge.
As the synthetical acid when repeatedly crystallised approaches the
habit of t h e storax acid, tho conclusion is drawn t h a t t h e former acid
is identical with the stoyax acid, but contains a small amount of an
impurity which is gradually removed by repeated crystallisation. The
presence of this impurity retards to an enormous extent the development of the crystals in the direction normal t o the face bf010).
By careful fractionation of the ethyl ester of the synthetical acid,
it has been found possible to isolate a fraction b. p. about 120/
0.2 mm., which when hydrolysed gives a n acid containing about
9% Cl. This acid is probably a n impure chlorocinnamic acid, and it is
shown t h a t when this impure .acid or when small amounts of either
0- or p-chlorocinnamic acids are added t o the acid from storax, they
alter its crystalline habit and transform it into the characteristic
crystals of the synthetical acid. The synthetical acid is thus the same

ORGANIC CHEMISTRY.

i. 175

acid as that from storax, but contains a small amount of a chloro-acid

which completely alters its crystalline appearance.
Erlenmeyer's hetero-acid contains a larger proportion of the chloroacid than does the synthetical acid.
Erlenmeyer states that specimens of benzaldehyde which are free from
chlorine yield the synthetical acid. It is shown that sinall amounts
(0.3%)of o-nitrocinnamic acid have the same effect on the crystalline
habit of the storax acid as larger amounts of the chloro-acids.
Erlenmeyer's a- and p-cinnamic acids are regarded as dimorphous
forms (compare Lehmann, Zeitsch. Kryst. Min., ltiS5, 10,339).

J. J. S.
Transformations
of
allo-Cinnamic and isoCinnamic
and H. TRUCKS&S(Ber., 1910, 43,
Acids. CARL LIEBERMANN
411-414.
Compare this vol., i, 36)-It
is shown that when
allocinnamic or isocinnamic acid of m. p. 58' is crystallised from
carefully rectified light petroleum (b. p. 30-40), crystals of the
iso-acid, m. p. 42O, can usually be obtained if proper precautions are
taken. The method consists in introducing a comparatively dilute
solution of the acid into a glass tube by means of a suitable funnel, and
then boiling the solution for some little time, so that the walls of the
tube are thoroughly purified, and also that the solution may he concentrated. The tube is then sealed, and when placed in ice-cold
water or in a freezing mixture, crystals of the acid m. p. 42" separate.
These occasionally become transformed into the less fusible acids
during transference from the tube.
J. J. S.

Mechanism of the Transformation of a-Hydroxy-py-unsaturated Acids into the Isomeric y-Keto-acids. ENILERLENNEYER (Festschrift Otto Vcdlach, 1909, 404--413).-A
discussion on
the course of the intramolecular rearrangement of a-hydroxy-,By-unsaturated acids into y-ketones (compare Frttig, Abstr., 1897, i, 14 ;
1898, i, 196), based on the author's investigations (compare Abstr.,
1898, i, 66s; 1903, i, 32, 414; 1904, i, 500, 892, 1025). W. H. G.

[Preparation of Triphenylmethane Colouring Matters from

Diortho-substituted Benzaldehydes.] ANILINFARBEN& EXTRAKTFABRIKEN
VORM. J . R. GEIGY (D.R.-Y. 213502.
Compare Abstr.,
19OS, i, 9S6).-1t has been shown previously t h a t the diortho-substituted benzaldehydes when employed in the production of triphenylmethane dyes yield colours of remarkable depth and fastness; it is
now found that these properties are enhanced when the two orthosubstituents consist of different halogen atoms. The following new
aldehydes are described :
2-Cidoro - 6 - brombenxaldehyde, prepared from 2-chloro-6-bromotoluene, forms colourless, spear-shaped crystals, m. p. 68".
2-Chloro-4: 6-dibromo-5-ciminobenzddehyde, m. p. 1 2 4 O , a colourless,
crpst,allinepowder, is obtained by the bromination in aqueous suspension
of 2-chloro-5-aminobenzaldehyde. 3 :4 : 6-T~-ibrowm
5-nminobennxaldehyde, m. p. 136-1 37". 2-Chloro-4 : Ij-dibrom,o-5-l~?/clro~~ybenznldel~~cle
crystallises in dark yellow needles, and has m. p. 116O.

F. M eG. M.

i. 176

ABSTRACTS OF CHEMICAL PAPERS.

p-Methoxysalicylaldehyde. PAUL
FRIEDLANDER
(Mornatsh.,1909,
30, 879 - 881).-Since
p-methoxysalicylaldehyde (o-hydroxyanisaldehyde), prepared by the action of sodium hydroxide on 4-methoxy-2keto-1-indoxylbenzene (compare Friedlander and Schuloff, Abstr.,
1908, i, 674), did not have the properties of the o-hydroxyanisaldehyde
described by Tiemann and Parrisius (compare Abstr., 1881, 270), the
compound has been prepared by the method employed by these
investigators, also by the action of methyl sulphate on 2 : 4-dihydroxybenzaldehyde, and found t o be identical with that derived from
4-methoxy-2-keto-1-indoxylbenzene.It is shown, further, t h a t the
substance obtained by Goulding and Pelly from Chlorocodon Whiteii
(Proc., 1908, 24, 62) is o-hydroxyanisaldehyde.
o-Hydroxyanisaldehyde has m. p. 41'; the oxime has m. p. 138';
the phenylhydrazone has m. p. 138' ; the aldaxine,
[OMe*C,H,(OH)*CH:N-I,,
W. H. G.
forins small, greenish-yellow crystals, m. p. 220.
Orthovanillin L2-Hydroxy-3-methoxybenzaldehydeJ
and its
Derivatives. FRANCIS
A. &I.NOELTING
(Bull. SOC.Ind. Xulhouse,
1909, 79, 401--430).-The
compound described by Tiemann and
Koppe as P-m-methoxysalicylaldehyde (compare Abstr., 1882, 54) is
definitely shown to be 2-hydroxy-3-methoxybenzaldehyde,
for, when
treated with acetic anhydride, i t yields 8-methoxycoumarin.
A large number of hydroxy- and methoxy-derivatives of benzaldazine and benzylideneaniline have been prepared with the object of
ascertaining the effect of these groups on the colour of the substance,
It is found that the para-derivatives of benzaldazine are the most
highly-coloured, whilst the ortho-substitution products of benzylideneaniline are more intensely coloured than the corresponding paraisomerides ; for example, vanillaldazine is golden-yellow, whilst 2-hydroxy - 3 - methoxybenzyaldazine is lemon-yellow ; 2-hydroxy-3-methoxy
benzylideneaniline is orange, whilst the 4-hydroxy-isomeride is pale
yellow. The ortho-, meta-, and para-hydroxy-derivativesof benzylideneaniline are lemon-yellow, white, and pale yellow respectively ; the
methyl ethers are all colourless, although the hydrochlorides are
lemon-yellow ; the methoxy-derivatives of the methyl ethers are not
coloured, although the introduction of a methoxy-group into the
hydroxy-derivatives increases the colour. Derivatives of benzylideneaniline containing a hydroxy- or methoxy-group are rendered
more intensely coloured by the introduction of a hydroxy-group.
2-Hydroxy - 3 - methoxybenzaldshyde crystallises in pale yellow
needles, m. p. 45*5",b. p. 265-266';
it dyes wool a n intense yellow,
and silk a pale yellow; the m. p.'s of various mixtures of this conpound with vanillin are recorded ; the sodium salt, C,H70,Na,H,0,
crys tallises in lemon-yellow plates ; the benzoate crystallises in small,
the oxime crystallises in white needles;
white needles, m. p. 74-75';
the phenylhydrazone, OMe*C,H,( O)-CH:N*NHPh, forms colourless
needles, m. p. 130-1 31 ; the phenyZmethy?hydraxoneforms colourless
crystals, m. p. 62'.
The methyl ether, C,H,(OMe);CHO, crystallises
in wbite needles, m. p. 52--53O, and dissolves in concentrated sulphuric
acid to a blood-red solution j the finely-divided substance produces

ORGANIC CHEMISTRY.

i. 177

violent sneezing ; the oxime has m. p. 98-99' ; the phenyZhydrazoae,

m. p. 1 3 8 O . is white. The parent substance couples with diazoC(CHO): CH --C *N,R
compounds, forming compounds of the type I
C(OH):C(OMe)'8H
'
and forms condensation products with the following bas'es, the colours
of which only are given : a-naphthylamine, scarlet ; P-naphthylamine,
crimson ; p-toluidine, orange ;p-anisidine, yellowish-orange ;p-pv-netidine, yellowish-orange ; o-chloroaniline, bright red ; dichloroaniline,
bright red ;p-nitroaniline, orange-red ;m-nitrotoluidine, orange-yellow ;
p-phenylenediamine, scarlet ; benzidine, brick-red.
0-JfetlLo~ybercxylidenean~Zine,
m. p. 44", is white ; the meta-isomeride
is also white ; 3 : 4-dihydroxybenxylide~ea~~tine,
m. p. 172', is bright
yellow, whilst the dimethyl ether, m. p. Sl", is white; 2-hydroxy-3methoxybeia~ytideneaniline,m. p. 84-85',
is orange, whilst the methyl
ether, m. p. 82.5", is white ; 4-hydroxy-3-methoxybenxylidenenniline,
m. p. 152-153", is pale yellow.
M -flydroxybenxaldaxine, m. p. 204-205O,
is pale yellow ; 2-l~ydroxy3-metl~ox,ybenxaZdczine,m. p. 198-1 99O, is lemon-yellow, whilst the
methyl ether, m. p. 151', is pale yellow.
Dimethylaniline condenses with 2-hydroxg-3-methoxybenzaldehyde
and 2 : 3-dimethoxybenzaldehyde, yieldiug 4' .4"-tetrarr~eti~ytdiamino2"'-h~droxy-3'''-methoxytri~hen~Zmethane,
m. p. 144O, and 4' : 4"-tetrarnetl~ylcliamino-2'":3"'dimethoxyt~~phenylmethcne,m. p. 130-1 31":
respectively j the hydrochlorides are green and bluish-green respectively.
8-l%?ethoxycoumarinforms inodorous, white crystals, m. p. 89".
W. H. G.

Iw. PETRENKOCarbonyl Group in the Nascent State. PAVEL

KRITSCHENKO
(J Buss. Phys. Chem. h'oc., 1909, 41, 1698--1703).-A
reply t o Stewart and Baly (compare Abstr., 1907, i, 220).
T. H. P.
Tetrabromocyclopentenedione. C. LORINGJACKSON
and H.
A. FLINT(Amer. Chem. J., 1910, 43, 135).--Jackson
and Russe
(Abstr., 1906, i, 290) found that by the action of fuming nitric acid and
bromine on tetrabromo-o-benzoquinone, two substances were produced,
one, yellow, m. p. 142q and the other, white, m. p. 144-146'.
The
present investigation was undertaken with a view to the further study
of these compounds.
The white substance could not again be obtained, but oxalic acid
was invariably produced.
The yellow compound has been found to be identical with Henle's
tetrabromocyclopentene-1 :3-dione (Abstr., 1907, i, 223), and is

yo

shown to have the constitution CO< CBr2*

It is readily decornCBrZCBr'
posed by boiling water or alcohol, but is remarkably stable towards
acids or oxidising agents, and can be boiled for several hours with
fuming nitric acid without undergoing visible change. When the
compound is treated with solution of sodium carbonate for several
days at the ordinary temperature, it is converted into dibromomaleic

i, 178

ABSTRACTS OF CHEMICAL PAPERS.

acid and methplene dibrornide. The action of sodium methoxide on

the compound also results in the formation of dibromomaleic acid.
By the action of aniline on tetrabromocyclopentene-1 :3-dione, there
are produced tribromoanili~zocyclopentenedione,
N H P h *C502Br3,m. p.
1 7 8 O , which crystallises i n yellow needles, and h,ydroxyanilinoccnalcyclopentenedione, NPh:C,O,(OH)*NHPh, which forms a dark red,
amorphous powder, and does not melt below 300'.
When tetrabromocyclopentenedione is reduced with sulphurons
acid, dibromodiketocyclopentene, C,H202Br,, m. p. 151', is obtained,
which crystallises in pale yellow plates, and, on treatment with
bromine, is reconverted into tetrabromocyclopentenedione. Phenylhydrazine reacts with dibromocyclopentenedione with formation of a
brown, amorphous substance, which does not melt below 300'. When
dihromocyclopentenedione is treated with aniline, bromoanilinocyclopentenedione, NHPh*C5H202Br,m. p. 121' (decornp.), is produced, which
forms slender, yellow needles, and is converted by sodium carbonate
solution into 1-anilino-A1-cyclopropen-3-one,
NHPh*C<

GO
I

CH'

m. p. 2.21'

(decomp.), which crystallises in yellow needles.

By the action of methyl alcohol on tetrabromodiketocyclopentene,
t r i b r o m o d i k e t o m e t h o x y c y c l o p ~ ~ e ~ e , ~ O M e ~ Cm.
5 0 ~p.B67O,
r ~ , is obtained,
which forms white, slender needles. The corresponding ethoxycompound, m. p. l l O o , crystallises in small, white needles, a i d is
converted by aniline into ?~yd~*oxydikls.toanilinocyclopentene,

NHPh*C,H,O,* OH,
m. p. 140' (decomp.), a red, amorphous substance, which yields a n cxcetyl
derivative, m. p. 150' (decornp.), as a pale brown, amorphous powder.
E. G.

Nitrosation of the Simplest Cyclic Ketones. WALTIIER

BOSSCHE
(Festschrift Otto Vallach, 1909, 301--312).-cycZoHexanone
is converted by amyl nitrite in the presence of a small quantity of
acetyl chloride into 1 : 3-dioximilzo-2-cycloAexano~,
CH *C(N-OH)
CH:2<(JH",C(N.0~)>co~
which crystallises in glistening, yellow needles, m. p. above 200'
(decomp.), and is decomposed by water, alcohol, and dilute acids ; the
corresponding triketone could not be isolated. The dioxime when
treated with a n alcoholic solution of sodium ethoxide and benzoyl
chloride yields a substance, C2,H2,0,Ns(?), crystallising i n colourless
needles, m. p. 92-93';
benzoylation in the presence of pyridine leads

CH gC(oBZ):N>CO
to the formation of a di6eraoate, CH2<CH:.C(C)Bz):N

(?), which

crystallises in slender, yellow needles, m. p. 170-172'

(decomp.), and
when boiled with a n aqueous solution ofi sodium hydroxide is probably
decomposed, thus : C,,H,,O,N, + 4NaOH = CN*CH2*CH2*CH2*CN
+
Na,CO, + 2Ph*C02Na+ 2H20. A n alcoholic solution of phenylhydrazine converts the dioxime into 1 : 2 : 3-triketocyclohexanet?.iphenyZhydmxoize, C24H24NG,
which crystallises i n slender needles, m. p.
182-IS3'.
The dioxime interacts with o-phenylenediamine, yielding

ORGAHIC CHEMISTRY.

i. 179

small, glistening, brown crystals, m. p. 216-218".

3 * 5-Dioximino-l-met?~yZ-4-cyclohexanone,
C7Hlo0,N2, prepared f roni
4-methylcycZohexanone, crystallises in pale yellow leaflets, turns brown
at 180', and decomposes suddenly a t 208'.
The following derivatives
are prepared by the methods just described : dibenxoate, small, pale
yellow needles, decomposing at 172' ; 3 : 4 :5-triketo-1-nzethylcycloILexanetriphenyl?bydraxone, C,,jH,,N,, small, slender, yellow needles,
m. p. 184' ; 1-oximino-3-rnetl~~2-l
: 2 ; 3 :4-teti*ahydrophenazine,
1'

qH1

,ON,,

small, glistening, yellow needles, m. p. 210-211*.

The parent
substance is converted (1) by a cold solution of phenylhydrazine in
glacial acetic acid into 3 ; 5-dioximi~ao-l-nzet?~~Zcyclohexa~z-4-one~hen,~lhyclruzone, C13HlG02N4,
a crystalline, orange powder, m. p. 220'
(decomp.) ; (%) an alcoholic solution of semicarbazide hydrochloride
and sodium acetate into the sernicarbnxone, C8H1303N5,which crystallises in spherical aggregates of small, colourless needles and decomposes at 200';
(3) by a n alcoholic solution of hydroxplamine
hydrochloride and sodium acetate into the corresponding Crioxime, a
colourless syrup, the dibenzoccte (1) of which, C21H1005N3,
crystallises
in small, colourless needles, m. p. 175'.
1 : 3-Dioxinzino-2-cyclopentanone,C5HA03N2,prepared from cyclopentanone, crystallises in flat, ysllow needles, and decomposes suddenly
at 215'.
W. H. G.

Catalytic Preparation of Aromatic Ketones.

JEAN B.
SENDEREMS
(Compt. rend., 19 10, 150, 111-1 12. Compare Abstr.,
1909, i, 286, 627 ; this vol., i, 11).-The following aromatic ketones
are readily obtained by the method already described, namely : acetoyhenone, propiophenone, phen yl propyl ketone, phenyl isopropyl
ketone, phenyl isobutyl ketone. To obtain a good yield, it is necessary to employ 3 mols. of the fatty acid to 1 mol. of benzoic acid, and
t o maintain the temperature of the catalyst at 380-460'.
The product is always accompanied by smaller quantities of the symmetrical
aliphatic ketone. Benzoic acid may be replaced by its anhydride.
W. 0. W.
Benzophenone could not be obtained by this method.

Additive Compounds of Ketones and Quinones with Acids

and Phenols. KURTH. MEYER(Ber., 1910, 43, 157-164.
Cornpare Abstr., 1908, i, $31 ; 1909, i, 395)-Whereas
acetophenone
only forms colourless double salts with metallic chlorides, benzophenone in many cases yields light yellow compounds. A yellow nitmte,
C1,l-I,,O*HN 0,, has been isolated, whilst the faintly yellow-coloured
solution of benzophenono in sulphuric acid undoubtedly contains a
coloured sulphate. Benzophenone has, although to a much less extent,
the same properties of halochrornism as distyryl ketone. The coloured
compounds of benzophenone could not be isolated, but those of
fluorenone ale more characteristic. Two series of double salts are
formed, the one a deep violet, represented by the compound with
aluminium bromide, and the other, mange in colour. The solution in

i. 180

ABSTRACTS OF CHEMICAL PAPERS.

sulphuric acid apparently cont,ains both forms, as the deep violet solution becomes orange-red on the gradual addition of water, and finally
colourless when the flmorenone separates.
Fluorenone also combines with phenols, forming deeply-coloured
products. W i t h a-naphthol, two compounds are formed : a n orangeyellow derivative from two molecules of fluorenone and one molecule
of a-naphthol, and a red substance from one molecule of each
component.
Similar compounds could not be obtained from distyryl ketone.
Disnisylideneacetone, however, disfolves in phenol with a n i n tense
yellow coloration, and forms with a-naphthol a crystalline, orangeyellow compound, containing three molecules of a-naphthol t o two
molecules of t h e ketone.
These compounds of ketones and quinones with phenols are
regarded as belonging to the same class of additive compounds as
those with acids, metallic chlorides, and sulphur dioxide. Both
classes possess a deep colour, pronounced crystallising power, and are
easily resolved into their components by water, or when heated i n
solvents ; their formation is exothermic. They are regarded as loose
additive products t o the quinonoid or ketone oxygen atom. Fluorenone
nitwcte forms orange-red needles ; the trichloroacetate gives orange
needles, m. p. 58' ; the mercurichloride, C13H80,(HgC12)2,
separates in
lustrous, orange needles. The stannichloride, (C,,H,O),,SnCl,, forms
brownish-yellow crystals. W i t h sulphur dioxide a substance crystallising in orange needles is obtained, containing between 1 and 14 mols.
of sulphur dioxide. Fluorenone aluminium b~ornide separates i n
dark red, almost black crystals. The compound, 2Cl,H,0,CloH,0,
produced on heating with a-naphthol, crystallises i n long, orange
needles, m. p. 66-67".
I n presence of a n excess of a-naphthol this is
converted into C,,H,O,CloH,O, separating in stout, red crystals,
m. p. 89'.
The compound of 2 mols. of disnisylylideneacetone and 3 mols. of
a-naphthol separates in long, orange needles, m, p. 69". Dirtnisylylideneacetone and sulphur dioxide form a n orange-yellow solution,
giving rise to orange-yellow needles when concentrated.
Phenanthrapuinone trichloroacetate, C,,H,O,,C,HO,Cl,,
crystallises in
E.F. A.
sealing-wax red needles, m. p. 138'.

Occurrence of P-Pinene and LPinocamphone in Hyssop

Oil, and S o m e Observations on Isomerides in the Pinene
Series. EDUARD
GILDERIEISTER
and HUGOKOHLER
(Festgchrgt Otto
Vallach, 1909, 41 4-43S).-An
account of part of this investigation
has appeared previously (compare Schimmel & Co., Abstr., 1908,
i, 666). I-Pinocamphone, obtained directly from hyssop oil, has b. p.
212-213'/752
mm., DZ 0.9662, nEo 1.47421, uD -13*7', whilst a
sample prepared by reducing t h e dibromide had b. p. 212.5-213*5'/
749 mm., D;: 0.9679, n1,5 1.47509, ng 1.47343, aD - 19.33'; the
dibromide has [u]: -49.26' in ether; the semicurbaxone has m. p.
228-229';
a small quantity of a second semicurbaxone, m. p. about
182-183',
was also obtained ; the oxime is a colourless oil, b. p.
105-1 10/4 mm., which deposits well-defined crystals, m. p. about

i. 181

ORGANIC CHEMISTRY.

37-38',
when kept for some time. The ketone is reduced by alcohol
and sodium, yielding I-pinocccmpheot, long, matted needles, m. p.
67-68',
b. p. 217-215",
uD - 44-63', [u]: -55.33" in alcohol,
Dt: 0.9678, ng 1.48420, nz 1.48335 ; the corresponding phenylurethane
crystallises in silky needles, m. p. 76-77'.
I-Phonic acid, obtained
by the oxidation of the ketone, is identical with t h a t described by
Barbicr and Grignard (compare Abstr., 1908, i, 852) ; when acted on
by concentrated sulphuric acid, i t yields 1-menthoethylheptanonolide,
crystallising i n rectangular plates, m. p. 46-47".
A n attempt t o prepare a pure active pinene by way of the crystalline xanthate, m. p. 36 -37',
derived from I-pinocampheol (compare
Tschugaeff, Abstr., lYOS, i, 93), led to the production of a mixture OF
pinene and a dicyclic terpene ; the latter, when oxidised, gave a
crystalline dicarboxylic acid, CI0Hl6O4,m. p. 192-193".
W. H. G.
Constituents of Ethereal Oils. Tetrahydrosan talene, Cl,H28.
FRIEDBICH
W . SEMMLER
(Ber., 1910, 43,445-448.
Compare Abstr.,
190'1, i, 431, 433, 1062 ; 1908, i, 433).--SantaZene dihydrochloride,
Cl,H,,,2HC1, obtained by the addition of hydrogen chloride to santalene
in methyl-alcoholic solution, has b. p. 140-142'/0.55
mm., D20 1.076,
and nD 1.4976. When distilled under 10 mm. pressure, it decomposes
to a certain extent, yielding hydrogen chloride, and, when boiled with
alcoholic potassium hydroxide, yields /3-santalene.
When the dihydrochloride is reduced with sodium and boiling ethyl
alcohol, it yields a mixture of hydrocarbons boiling a t 119-123'/9
mm.
The unsaturated hydrocarbons may be removed from this mixture by
treatment with ozone, when pure tetrahydrosantalene, Cl,H28.is obtained.
It has b. p. 116-115/9 mm., D20 0.564, n, 1.4676, atid a, +7'30'
(100 mm. tube). The hydrocarbon must be dicyclic, as i t has all t h e
properties of a saturated compound ; it is thus analogous to 'dihydroeksan talol and dihydroeksantalic acid.
J. J. S.

Action of Magnesium and Ally1 Bromide on Menthone.

P. RYSCHENKO
(J. Rum. Php. Chem. Xoc., 1909, 41, 1695-1698
Compare Javor sky, A bstr ., 190 9, i, 16 8).-1- rMe thy Z-4-iso~ropy Z-3-allyZcycloi~exan-3-oZ,G H , < ~ ~ ~ ~ ~ ~ ~ > C ( C H , * C H : C H ,obtained
) * O H ,on
decomposing by means of water the Grignard compound yielded by
magnesium, ally1 bromide, and menthone, is a mobile, colourless liquid,
b. p. 130-131/22 mm., Di7 0.9028, n 1.470035, with an odour like
that of mint. On oxidation with permanganate, it yields (1) mentholacetic acid, C

HCHMe-CH2>C(CH,*C0,H)*OH,
~
<
~
~
~
. which,
~ when
~ heated
~
~

with potassium hydrogen sulphate, loses water and gives an acid,

C12H,,02; both of these acids were obtained by Wallach (Abstr., 1902,
i, 799) ; (2) the trihydric alcohol,

CH,<~~~~~~;>C(OH)-CH,=CH(OH)-CH,-OH,
T. B. P.
which is a pale yellow, syrupy, odourless liquid.
VOL. XCVILI. i.

i. 182

ABSTRACTS OF CHEMICAL PAPERS.

Behaviour of Alicyclic Hydroxylamines and Hydroxylamineoximes towards N i t r o u s Acid.

I. GUIDO CUSMANO
(Gazxetta, 1909,33, ii, 453-467.
Compare Francesconi and Cusmano,
Abstr., 1909, i, 723, 724).-isoNitroamines
form two classes of
ethers : (1) NO-NR-OEt', which readily give up nitrous acid, and
R*fl:N*OR RON-N*OR
or
\/
, which, under similar conditions, are
(2)
0

0
either stable or else yield nitrous oxide. Analogous behaviour is
shown by the two classes of ether formed by the nitroamines, namely,
(1) NO,-NRR, which decompose, giving nitrous acid, and

R*N:R*OR R*N-N*OR'
0
or
\/
>
0
which yield nitrous oxide. It seems, then, that in these ethers the
can be completely eliminated from the forms
complex -N,O,-N:N*O- N:R*O*
*N-N*O*
,
, and \ / , but not from the forms -N(NO,)0
and -N(NO)*O-. Hence the nitroamines and isonitroamines, which in
the free state probably possess the forms R*NH*NO,and R*N(OH)*NO
(2)

respectively, retain these forms when they decompose with elimination

of nitrous acid, but assume the forms R*N:NO*OH and R*NO:N-OH
when decomposition is accompanied by separation of hyponitrous acid
or nitrous oxide and water. As a rule, the known isonitroamines
exhibit one or other of the above two methods oE decomposition, but
the author finds that, by varying the conditions, pulegonenitrosohydroxylamine (menthoisonitroamine) can be decomposed in both ways,
and can hence react in the two forms :

C H M e < ~ ~ ~ < ~ > C H * C M e 2 * N ( N Oand

)*OH
CHMe<~~~~~>CH*CMe,*NO:N*OH.
By the action of hydroxylamine o n Apulggone, three compounds
have been obtained : pulegonehydroxylamine, m. p. 154' (compare
Beckmann and Pleissner, Abstr., 1891, 936), a n oxime, m. p. 120'
(compare Wallach, Abstr., 1896, i, 309), and [a] pulegonehydroxylamiheoxime, m. p. 118' (compare Semmler, Abstr., 1905, i, 222).
The author has obtained two new derivatives of pulegone, namely, an
oxime, m. p. 98', and a [/3] hydroxylemineoxime, m. p. 143'. Wal!ach
(Terpene und Campher, Leipzig, 1909) regards the oxime m. p. 120' as
a n oxime of isopulegone, and the oxime m. p. 98' is either stereoisomeric with this,

CH -CH >C:CMe,
C H M e < ~ ~ ~ ~CMe,
~ > C : cHMe<CH~--C
and
#*OH
0H-H
or structurally isomeric,

The new hydroxylamineoxime, m. p. 143', is stereoisomeric with t h a t

i. 183

ORGANIC CHEMISTRY.

described by Semmler (Zoc. cit.), such isomerism being due either to

the oximic nitrogen, thus :

or to the method of rupture of t h e double linking of pulegone and the

subsequent addition of hydroxylamine, thus :

Pulegoneoxime, C,,H,,:NOH, m. p. 98", prepared by the action of

hydrochloric acid on isopulegoneoxime, m. p. 120, forms groups of
lamias with triangular sections, reduces Fehling's solution, and is
rapidly decomposed by heating with dilute sulphuric acid, but is not
affected by boiling with alcoholic potassium hydroxide.
p-Pulegonehydroxylamineoxime,GlpHzoO2Nz, which is obtained
together with the a-isomeride and zsopulegoneoxime when pulegone
and hydroxylamine react under certain conditions, forms shining
needles, m. p. l43', reduces Fehling's solution instantaneouFly in the
cold, and, when dissolved in organic solvents, is oxidised by the air to
nitroso-compounds of a blue colour.
Pzlle~onenitrosoldroxylarnine,
prepired by the action Lf niirous acid on pulegonehydroxylamine,
forms irregular, hexagonal crystals, m. p. 35" (decomp.), gives
Liebermann's and the diphenylamine reactions, and in ethereal or
alcoholic solution gives a garnet-red coloration with ferric chloride ; it
does not reduce Fehling's solution, but forms a semicarbaaone,
NH,~CO~NH~N:Cl,H17*N(~O)*OH,
m. p. 165" (decomp.), which gives
Liebermann's and the diphenylamine reactions and a red coloration
with ferric chloride. With hydroxylamine in alcoholic solution, pulegonenitrosohydroxylamine gives a white, hygroscopic substance, decomp.
at 200, which reduces Fehling's solution in the cold and gives
Liebermann's reaction, but gives no coloration with ferric chloride.
When suspended in water or dissolved in organic solvents, pulegonenitrosohydroxylamine is moderately stable, but in the dry state in the
air, or in a vacuum, it undergoes rapid decomposition, yielding (1) pulegone and (2) 8-nitromenthone (compare Harries and Roeder, Abstr.,
1900, i, 182), which results from the oxidation of the &nitrosomenthone formed initially by the action of the air and of the nitric acid
eliminated. With nitrous acid, pulegonenitrosohy droxylamine gives

0 2

i. 184

ABSTRACTS OF CHEMICAL PAPERS.

pulegone and nitro- and nitroso-menthones. The last two compounds

are formed according to the equation :
CioE,~O*NH*OJ3
+ CloH,~O*N(NO)*OH
+ HNO, =
C10H170*N02
+ CioHl~O*N,O+ N, + 2H,O.
The formation of pulegone by the action of nitrous acid is due to the
diazotisation of the pulegonenitrosohydroxylamine, thus :
Ci,H,70*N(NO)*OH + HNO, = ClpHJ70*N2*N0,
+ H20 ;
the resulting aliphatic diazo-derivative is immediately decomposed by
water into nitrogen, nitric acid, and 8-hydroxymenthone, the last compound then losing water and giving pulegone. When, however,
decomposition of pulegonenitrosohydroxylamine occurs in presence of
an alkali, it proceeds entirely i n the one direction, the resultant
products boinipulegone and niirous oxide : C,,H,,O*NO:N*OH + H,O =
C,,Hi70*OH + H20+ N,O and C,,H,,O*OH = Cl,Hi,O + H20.

T. H. P.

New Occurrence of I-Camphor.

THEODORWHITTELSEY
(Bestschr@ Otto WaEIach, 1909, 668--670).-The
oil obtained from
a variety of sage-brush common to western North America,
probably Artemisia cana, was found to have the following constants :
DE O*94Ot5; a: - 19.09; rig's 1.4702 ; acid number, 4.2, 4.2 ; est,er
number, 18.5, 19.8 ; saponiEcation number, 22-7, 23.9 ; saponification
number after acetylation, 111.8, 110.3. It contains kcamphor to the
extent of at least 44.5%, an observation not without interest, for,
with the exception observed by Wallach in the case of the broadleafed Sulvia, I-camphor has been found only in plants of the family
Conzposit ae.
W. H. G .
C o r i a n d e r Oil. HEINRICH
WALBAUM
and WILHELMM ~ L L E R
(FestschriJt Otto Wu,IZach, 1909, 654-667).-The
sample of coriander
oil examined had the following constants: Di! 0.8735; aD +10*4O;
nz 1.46387; acid number, 0 ; ester number, 20.22; ester number
after acetylation, 159, corresponding with 49.65% of linalool; it is
possible to obtain, however, 70% of the latter substance by fractional
distillation on a large scale. Roughly, 20% of the oil consists of
almost equal quantities of a-d-pinene,p-cymene, and terpinenes (a-and
y-terpinene), together with very small quantities of /3-pinene, dipen tene,
and possibly, also, qhellandrene and terpinolene. The presence of
decylaldehyde, geraniol, I-borneol, and esters of these alcohols was
also established. I n addition to the compounds mentioned, coriander
oil contains small quantities of unknown substances, which are of
W. H. G.
importance in imparting aroma t o the oil.

FILS(Sci.Ind. Bull. Roure[Essential Oils.] ROURE-BERTRAND

Bertrand FiIs, 1909, [ii], 10, 19-43).-This
contains the following
new work :
[JUSTIN
DUPONT
and LOUISL A B A u N E . ] - ~ ~ ~ oof~ Hydrochloric Acid
on, LincsZooI and Geraniol (compare Grosser, Abstr., 1882, 525 ;
Barbier, ibid., 1892, 1236 ; 1895, i, 7S).-When dissolved i n tduene
and treated with gaseous hydrogen chloride at loo, both alcohols
yield Iinalyl chloride, CIoHi7CI,D20 0.9341, [a]: 1-50, fi: 1.4813, and
b. p. 95---96/6 mm. This on treatment with silver nitrate in alcohol

ORGANIC CHEMISTRY.

i, 185

regenerates linalool. The chloride obtained from geraniol could not

be obtained quite pure. At -4' to + 3 O the action of hydrogen
chloride on linalool or geraniol in toluene is more complicated. No
water is formed until the mixture regains atmospheric temperature.
The product formed is a mixture of linalyl chloride with a dichloroderivative. Cinnamyl alcohol a t 100' yields a chloride, C,H,Cl,
D22 1.0857, ng 1.583, b. p. 115-116'/6
mm., which absorbs bromine,
forming a dibromide, m. p. 104', and on treatmentwith silver nitrate i u
alcohol yields a mixture of two alcohols, one of which may be
phenylallyl alcohol (Klages and Klenk, Abstr., 1906, i, 638).
[J. J J ~ ~ o ~ ~ ~ . ] - P r e p a ~ c 6otfi openc?bone
n
free f y o m Camphor.-The
best results were obtained by warming crude fenchone with aluminium
chloride and then distilling under reduced pressure. For the detection
of camphor the semicarbaxide test was employed, which is sufficient to
show the presence of 0.1% of camphor. By this means camphor wacj
proved to occur naturallyin fennel oil. Thujone cannot be eliminated
from mixtures of this ketone with camphor and fenchone by treatment
with aluminium chloride and bromine, and in such cases oxidation
with nitric acid must be resorted to, the camphor being subsequently
removed by treatment with aluminium chloride and bromiue.
Four oils from the Comores Islands were examined, and gave the
following results : Bigarade oil had D15 0.8812, a, + 42'13', and was
insoluble in 80% alcohol.
Petitgrain oil had D15 0 8650, a,, + 42'18', and saponification value
33.6.
Basil oil had DI5 0,9588, U, 0'35', and saponification value 4.2.
Citronella oil had D15 0.8922, a , -Oo52', aldehydes 80% (by
bisul phite process), and was insoluble even in absolute alcohol.
Ylang-ylang oil, from Nossi-BQ, had D15 0.9673, a, - 42'12', acid
value 1.4, saponificatiori value 129.5, esters 45.3%, and total alcohols
42 .i.%.
Linaloe oil, from Cayenne, had D20 0.8721, aD - 12'56', nz 1.4635,
and contained methylheptenone, d-terpineol, geraniol, I-linalool, and
T. A. H
nerol (?).

Constituents of Oil of Lemon. EDUARDGILDEMEISTER

and
WILHELX
MULLER(FestsdWt~tOtto Wallach, 1909, 439-451).-0il
of
lemon contains in addition to E-limonene a moderate quantity of
I-P-pinene, and very small quantities of a-pinene, i-a-pinene, I-camphene,
/3-phellandrene, and y-terpinene. The sesquiterpene obtained from the
oil in small quantity (compare Burgess and Page, Trans., 1904, 85,
414) is shown to be identical with bisabolene (compare Tucholka,
Abstr., 1897, ii, 584); the same hydrocarbon is present i n opoponax
oil, oil of Piper Yolkensii (compare Schmidt and Weilinger, Abstr.,
1906, i, 299), and camphor oil.
The erythritol from y-terpinene (compare Wallach, Abstr., 1908, i,
814) undergoes the following changes : (1) when boiled with acids it
yields a mixture of thymol and carvacrol ; (2) it yields a brominated
substance, crystallising in large leaflets, m. p. 93-94O, when treated
with an alkaline solution of hypobromite ; (3) when oxidised with a n

i. 186

ABSTRACTS OF CHEMICAL PAPERS.

alkaline solution of potassium permanganate it yields oxalic acid and

a n acid, m. p. 147-149',
which is probably isopropyltartronic acid.
W. H. G.

Essential Oil from the Seeds of Monodora grandiflora.

ROBERTLEIMBACH
(Festschrift Otto FFaZZach, 1909, 502-512) .--The
oil obtained by the steam distillation of the seeds of Monodorcl
grandayora is a limpid, pale yellow oil, with an odour resembling
cymene, D: 0.85'74, :a - 46.25' in ZL l-dcm. tube, acid number 3.9,
saponification number 7-12.
Nearly 900/, of the oil consists of
hydrocarbons, chiefly Z-phellandrene, camphene, and p-cymene. The
remainder, a heavy oil with an aromatic odour, contains palmitic acid,
carvacrol, a substance, C,,H,,O, which reacts neither as a n alcohol nor
a ketone, a sesquiterpene, C15H24,b. p. 260-270, I):; 0.9138, aD + 24O,
n1,6 1.50513, a crystalline substance, m. p. 160-1663',
and small
W. H. G .
quantitias of other unknown substances.

A Condensation Product of Coumaranone and its Conversion into Oxindirubin. KARLFRIESand W. PFAFFENDORFF
(Bey., 1910, 43, 212--219).-The
constitutions have been ascertained
of the compound, C,,H,,O,, obtained from 4-methyl-2-coumaranoneor
from w-chloro-2-hydroxy-5-methylacetophenone
(Abstr., 1909, i, 44),and
also of those obtained by a similar process from 5-methyl-2-coumaranone or w-chloro-2-hydroxy-4-methylacetophenone,
and from 2-coumaranone or o-chloro-2-hydroxyacetophenone. A n ethereal solution of
2-coumaranone is treated with sodium and then with acetvl chloride,
whereby the acetute, m. p- 106", of 2-hydroxy-1 : 2'-dicoumarone,
is formed ; the parent substance has
CH*O '
not been obtained pure. By warming an alcoholic solution of the
acetate with sodium ethoxide and subsequently acidifying, by boiling
a n acetic acid solution of the acetate with hydrogen peroxide, or by
the prolonged heating of 2-coumnranone or o-chloro-Z-hydroxyacetoDhenone with alcoholic sodium ethoxide, 2 : 1'-dihvdroxu-1 : 2'-dicounaar-

C6H4<30H)>c*c<C6B4

is obtained, which forms orange-yellow needles, gives a deep red, nonfluorescent solution in concentrated sulphuric acid, and by the
prolonged heating of its solution in glacial acetic acid, or, more readily,
by treating the solution with hydrogen peroxide or bromine, is converted into '' 1 : 2-biscoumaran-indigo " (oxindirubin),
m. p. 215", which is also obtained by treating a n acetic acid solution
of 2-coumaranone and o-hydroxybenzoyl formic acid with concentrated

sulphuric acid.
By a similar series of reactions, 5-methyl-2-coumaranone yields the
acetate, m. p. 133O, of 2-hydroxy-5 : 5'-dimethyl-1 : 2'-dicoumarone,
2 : l'-dihydroxy-5 : 5'-dimethyl-l : 2'-dicoumarone (5 : 5'-dirnethyl-leucooxindirwhin), m. p. 204O, and '' 1 ; 2'-bis(5-methylcoumaran)-indigo
"

ORGANIC CHEMISTRY.

i. 187

(5 :5'-dimethyZoxindirubin). The compound CI8Hl4O4 (loc. cit.) is

4 :4'-dimethyl-lenco-oxindirubin.
c. s.
Oxonium Perchlorates. KARLA. HOFMANN,
A. METZLEB,
and
H. LECHER
(Ber., 1910, 43, 178-183.
Compare Abstr., 1909, ii,
568).-Seventy per cent. perchloric acid yields crystalline compounds
with ketones, and similar substances with basic properties ; these are
sparingly soluble and admirably adapted for characterising and
isolating ketones. Even substances, such as carbazole, in which the
basic properties of the nitrogen are very feeble, form crystalline salts.
The perchlorates afford a better test of basic properties than picrates.
These salts are regarded as oxonium derivatives.
A solution of xanthone in tetrachloroethane gives a bright yellow
precipitate of xanthone perchlorate, C13H802,HC104, which can be
recrystallised from tetrachloroethane without decomposition, but is
very rapidly decomposed by traces of moisture.
Carbaxole perchlorate crystallises in lustrous, colourless plates ; it is
decomposed by water. Prolonged action with an excess of perchloric
acid leads to the formation of a greenish-blue compound.
A colourless perchlorate is also formed by quinone di-imide. This
explodes on heating. When moistened with water, it becomes a
brilliant bluish-green, then violet, and then brown.
Benzophenone forms a yellow solution and a bright brownish-yellow,
crystalline mass. This rapidly decomposes in moist air, leaving
colourless oily drops, which do not crgstallise until inoculated with a
crystal of benzophenone. The perchlorate is apparently derived from
the allotropic low melting variety of benzophenone.
Anthraquinone and alizarin do not react with perchloric acid,
Phenanthraquinone perchlorate forms a mass of blood-red crystals in
solution, which dry t o red needles, but rapidly become bright orange
when exposed t o moist air. The hemiperchlorate, (C,4H,0,)2,HC104,
is obtained in flat, obliquely-cut, yellow or brownish-red prisms.
From retenequinone only the hemiperch2orate has been isolated.
Naphthazarin perchlovate forms large, rectangular, stout plates with a
bronze lustre.
E. F. A.
4

New Selenium Compound. IDAFOA(Gaxxetta, 1909, 39, ii,

527-534).-XeZenophen,

S.'H:CH>Se, obtained by heating sodium

CH:CH
succinate with phosphorus triselenide, is a yellow, mobile, irritant
mm.; i t dissolves in concentrated
liquid, b. p. 147-149'/250
sulphuric acid, giving a reddish-brown coloration, whilst with a
solution of isatin i n concentrated sulphuric acid, a dark carmine
coloration is obtained. I n presence of acetic acid, it forms with
T. H. I?.
bromine a n unstable, liquid bromide.

Production of a Volatile A r o m a t i c S u b s t a n c e from Solutions

of Morphine Salts. C . REICEARD
(Pharnz. 2entr.-h., 1910, 51,
128--130).-Then
a solution of morphine hydrochloride or sulphate
in water is heated, a slight odour of musk is developed, aud the

i. 188

ABSTRACTS OF CHEMICAL PAPERS.

strength of this odour increases with the concentration of the alkaloidal

solution, and with the quantity of water vapour produced from
T. A. H.
t h e solution.

Partial Racemism. H. DUTILH

(I'roc. K . Akad. Tetensch. Amsterdam, 1909, 12, 393-400).--The
author has studied the partial
racemism which occurs with strychnine racemate, more especially by
observing the behaviour of this compound in presence of its aqueous
solution. The investigation was carried out on the lines indicated by
Roozeboom (Abstr., 1899, ii, 401), who pointed out t h e probable
inaccuracy of the results obtained by Ladenburg and Doctor (Abstr.,
1899, i, 310). By means of the solubility curves of the d-, I-, Z + r - ,
and d + r-compounds at 40, 25', 16', and 7*5', i t mas found that the
transition interval, which Ladenburg and Doctor assumed to be nonexistent, extended over about 20'.
Saturated solutions of the partial
racemate are stable only below 75", although the solubility at higher
tsmperstures can be determined by retarding the decomposition.
The author has avoided determining by means of the polmimeter
the content of the I- and d-compounds in liquids saturated with the
r + d - , r + Z - , or d+I-compounds, and suggests t h a t such method of
analysis gives a wrong idea concerning the inner composition of
a solution saturated with two salts. This view is supported by the
results obtained by Findlay and Hickmnns (Trans., 1909, 95, 1386),
who, using the polarimetric method of estimation, found t h a t the
addition of I-menthyl Emandelate diminishes t h e solubility of I-menthyl
d-mandelate at lo', whilst it increas'es i t a t 25' or 35' ; such behaviour
the author regards as improlmble.
T. H. P.
H m m o p y r r o l e . LEONMARCHLEWSKI
(Ber., 1910,43, 259-260).R.V. S.
Polemical, A reply to Piloty (chis vol., i, 133).

Pyridine Hydrate. WILLIAMOECHSNERDE CONINCK(BUZZ. SOC.

chim. Belg., 1910, 24, 55).-From basic t a r oils the author has isolated
a product which has the composition of a pyridine hydrate,
SC,H,N,7H20.
This has b. D. 91-93',
but it is not regarded as a definite chemical
compound (dompare Goldschmidt and Coistam, Abstr., 1884, 611).
T. A. H.
Condensation of Esters of Acetonedicarboxylic Acid
with Aldehydes by means of Ammonia and Amines. VI.
Tautomerism of Ethyl 2 :6-Diphenyl-4-pyridone-3: 5-dicarband JOH. SCIIOTTLE
oxylate. PAVEI;Iw. PETRENKO-KRITSCHENKO
(Bey., 1910,43, 203--206).-The
methylation of ethyl 2 : 6-diphenyl-4pyridone-3 : 5-dicarboxylate i n alkaline solution leads to t'he formation
2 : 6-diphenyl-1-methyl-4-pyridone-3
: 5-dicarboxylic acid, m. p.
270, and a mixture, m. p. 125-130O (Abstr., 1909, i, 605). By hydrolysing the latter by 7% aqueous alkali and mbsequent acidification, a n
acid, C,,H,,O,N, is obtained, which separates from dilute acetic acid
in crystals, m. p. 240' (decomp.), containing 14C,H,02,. and forms a n
ethyl ester, m. p. 229-230,
which is insoluble in ammonium
of

i. 189

ORGANIC CHEMISTRY,

hydroxide. The acid is probably 4-methoxy-2 : 6-diphenylpyridine

3 : 5-dicarboxylic acid.
c. s.

Anthranil. XVI. Relation of Anthroxanic Acid (2Anthranilcarboxylic Acid) to Anthranil. EUGENBAMBERGER

and SVEN
LINDBERG
(Bey., 1910, 43, 122-127.
Compare Abstr., 1909, i, 509,
510, 5 1I).-o-Amino- and o-nitro-aromatic aldehydes and ketones are
converted by mild oxidising and reducing agents respectively into
anthranil derivatives. To establish the constitution of anthroxanic
--the
acid as anthranil-2-carbouylic acid, C H
* C(C0,H)>O,
behaviour of isatinic acid and o-nitrophenylglyoxylic acid has been
studied.
By the oxidation of isatinic :acid with Caro's reagent, anthroxanic
acid, 2 : 2'-azoxybenzoic acid, and o-nitrosobenzoic acid are formed.
The last product affords strong support t o the view that o-hydroxylaminophenylglyoxylic acid, OH*NH*C,H,*CO*CO,H, is the first
intermediate oxidation product.
o-Nitrophenylglyoxylic acid, when reduced by tin and acetic acid,
forms anthroxanic acid and a compound, m. p. 127O, probably 1-acetyl-

<;y

dioxi ndole,

C , H 4 < ~ ~ ~0.~ ~ & ~ c

E. F. A.

Cinchonic Acid Syntheses. WALTHER

BORSCHE
(Ber., 1910,43,
reply to Schiff (this POI., i, 134).
R. V. S.

267).-A

Elimination of Alkyl Radicles and Fission of Organic

Bases by means of Cyanogen Bromide and Phosphorus
Halides. JULIUSVON BRAUN(Festschrgt Otto Wullach, 1909,
313--386).-A
rdsum6 of the author's investigations on this subject
(compare Abstr., 1904, i, 688, 731, 841, 918; 1905, i, 596, 634, 636,
826; 1906, i, 576; 1907, i, 28, 79, 105, 110, 127, 151, 524, 728, 899,
960 ; 1908, i, 625, 627, 675, and 685). The following observations
have not been recorded previously. Quinoline is converted by
cyanogen bromide and water into a crystalline substance, m. p. 113",
CH=$!H
which probably has the formula C,H4<
.
N (CN);-,CH*OH'
Benzoylhexahydrocarbazole and the 4-methyl compound (compare
Borsche, Abstr., 1908, i, 365), when acted on by phosphorus chloridep,
yield 2-benxoyZnminodiphenyl, m. p. 102O, and 2'-benxoylamino-4-methylW. H. G.
diphenyl, m. p. 12l0, respectively.

Indigoid Dyes. V. Indigoid Dyes of the Anthracene

and PAULFRIEDLANDER
(Monatsh., 1909, 30,
Series. A. BEZDZIK
871-878.
Compare Abstr., 1909, i, 415, 417)-Isatin
chloride and
isatinanilide condense with hydroxy-derivatives of anthracene, forming
indigoid dyes, which are far more stable towards acids and alkalis than
the analogous naphthalene compounds (compare Abstr., 1908, i,
673) ; for example, 1-keto-2-indoxylanthracene is not decomposed by
sodium hydroxide, although the isomeride, 2-keto-l-indoxylanthracene,
when similarly treated yields anthranilic acid and 2-hydroxy-

i. 190

ABSTRACTS OF CHEMICAL PAPERS.

1-anthracenealdehyde. The latter substance has the property of

dyeing animal fibres and the skin a n intense yellow :
1-Keto-2-indoxykanthrucene(I), prepared b;jl the condensation of
a-anthrol and isatinanilide in acetic anhydride, crystallises in small,
dark blue needles with a bronzy reflex, melts and sublimes with
decomposition at a high temperature, and, when reduced with an
alkaline solution of hyposulphite, yields a n orange-red solution which
dyes textile fibres a pure blue.
2-Keto-1-indoxylunthracene (11),similarly prepared from /3-anthrol,
forms small, dark blue needles with a coppery reflex, and sublimes with
decomposition at a high temperature. 2-Hydroxy-l-unthracenealdehyde,
C15HloOz,crystallises i n long, pale yellow needles, m. p. 16-1' ; the
oxime crystallises in four-sided, pale green plates, m. p. 197' (decomp.) ;
the phenylhydrazone forms flat, yellow prisms, m. p. 224-225';
the
cddazine forms slender, brick-red needles, m. p. above 3 0 0 O .
5-Bydroxy-l-keto-2-indoxylanthrucene,C,,H,,O,N,
prepared from
1 : 5-dihydroxyanthracene and isatin chloride, crystallises in long,
slender, dark blue needles ; tbe isomeric 8-hydrozy-compound is very
W. H. G.
similar in properties, but is slightly more green.

Synthesis of Oxazoles and Thiazoles. I. SIEGMUND

GABRIEL
(Ber., 1910, 43, 134--138).-By
the action of phosphorus pentacbloride on benzoylaminoacetophenone, 4-chloro-2 :5-diphenyloxaxole is
formed, and not a chlorinated isoquinoline derivative, as might be
expected from analogy t o the synthesis of dihydroisoquinolines from
acyl derivatives of phenylethylamine.
w-Benzoylaminoacetophenone is best prepared from w-aminoacetophenone hydrochloride by the action of benzoyl chloride in acetic acid
solution; it has m. p. 124' [Robinson, Trans., 1909, 95, 2169, gives
123'1. When heated with t w o mols. of phosphorus pentachloride,
first at the temperature of the water-bath and later to 1709 4-chloro2 : 5-dipherzyloxacxoZe, O < c P h ~ ~'l, is formed, crystallising in slender
CPh.N
When heated with sodium amalgam in

needles, m. p. 67-68'.

alcoholic solution, 2 : 5-diphenyloxazole, O<

CPh:vH,

is obtained (comCPhX
pare E. Fischer, Abstr., 1896, i, 262). The same compound may be
obtained in one operation from benzoylaminoacetophenone when only
one molecule of phosphorus pentachloride is used. Similarly, when
benzoylaminoacetophenone and phosphorus pentasulphide are heated a t

170, 2 :5-diphenyZthiaxoZe, S<CPhi(?K, is formed, cry stallising in

CPh.N
large, rhombic plates, m. p. 103-104'.

E.F. A.

Action of Hydrazines on Thiocyanoacetic Acid and its

Ethyl Ester. GUSTAVPRERICHS
and PAULFORSTER
(AnnaZerz, 1910,
371, 227-257).-The
nature of the interaction of thiocyanoacetic
acid and phenglhydrazine as described by Harries and Klamt (Abstr.,

ORGANIC CHEMISTRY.

i. 191

1900, i, 413) not being strictly analogous to t h a t of thiocyanoacetic

acid and aniline (compare Rizzo, Abstr., 1898, i, 6 5 9 ; Beckurts and
Frerichs, Abstr., 1902, i, 763), it was deemed advisable t o repeat the
work of the first-named investigators, the outcome of which has been
the direct negation of many of the statements of these authors.
When phenylhydrazine is added to a cold ethereal solution of tbiocyanoacetic acid, a white, crystalline precipitate of phenylhydrazine
thiocorbimidoacetate, SCN*CH,*CO,H,NH,*NHPh, m. p. 92-looo, is
obtained, which, when kept for some time, or when boiled with alcohol,
passes into corbaminethiogZycoZZpheny2hydraaide,

NH,*CO*S*CH,*CO*NH*NHPh,

colourless leaflets, m. p. 149O. The latter substance is more readily

obtained by the interaction of phenylhydrazine, chloroacetic acid, and
potassium thiocyanate in alcoholic solution ; when heated at about
155 for a n hour, it passes into d i t h i o d i g Z y c o Z Z p h ~ n ~ Z ~ ~ y d r a ~ ~ ~ e ,
S(, CH,. CO*NH*NHPh),,
which crystallises in colourless, glistening leaflets, m. p. 174, and is
also formed by heating carbaminethioglycollphenylhydrazidewith 10%
aqueous ammonia and treating the solution subsequently with hydrogen
peroxide.
When ethyl thiocganoacetate is boiled with a n alcoholic solution of
phenylbydrazine, it yields ammonium cyanate, a viscid, oily substance,
and 3-aniZinothiohydantoin, Z G i Z > N * N H P h , colourless crystals,
m. p. 176O, which dissolve in concentrated sulphuric acid and aqueous
potassium hydroxide, forming blue and violet solutions respectively ;
the substance just described is also formed by the action of phenylthiosemicarbazide on chloroacetic acid. The interaction of chloroacetylphenyleemicarbazide and potassium thiocyanate in alcoholic
solution leads to the formation of thiocarbimidoacetylphenylsemicavbaxide, SCN*CH2*CO*NPh*NH*CO*NH2,
small, glistening crystals,
m. p. 172-173, which, when boiled with water, yields 2-hnino-5-kelo-

4-phenyltetrahydro-1 : 3 :4-thiodiaxinc, S< C(NH)*NH>WPh, crystalCH,-CO

lising in pale yellow needles, m. p. 161-162O; the crystalline salts
with the halogen acids, C,H,ON,S,HX, were prepared.
Hydrazine hydrate and thiocyanoacetic acid combine, yielding
hydvazine thiocarbimidoacetate, SCN*CH,*CO,H, N,H,, glistening leaf lets, m. p. 87-90, which undergoes intermolecular rearrangement
when kept, passing probably into carbaminethioglycoZZhydyaxide,

NH,*CO*S*CH,*CO*NH*NH,,
m. p. about 125, and, when boiled with water, yields a substance,
which decomDoses at 280-2909 and could not be obtained Dure. The
action of hidrazine hydrate 0; ethyl tbiocyanoacetate l&ds to the
yH,-CO
CO-YH,.
formation of 3 : 3-bisthiohydantoin,
S*C(NH)>N<C(NHPS

the same substance is formed by the intekctibn of bisthiocarbamide

(hydrazodicarboxythioamide) and chloroacetic acid ; it decomposes
without melting a t a high temperature.
Carbaftninethioglycollphenylhydrazide undergoes the following

i. 192

ABSTRACTS OF CHEMICAL PAPERS.

changes : (1) when boiled with 10% aqueous ammonia and subsequently treated with hydrochloric acid, it yields thioglycollphenylhydraxide, NHPh*NH*CO*CH,*SH,leaflets, m. p. 112-113' ; (2) it
is converted by alcoholic potassium hydroxide and methyl iodide under
pressure at 100' into rnethyZthiogZycoZZphenylhydraxide, CgH,,ON,S,
glistening leaflets, m. p. 104-105 ; the corresponding ethyl compound,
C,,H,,ON,S, forms colourless leaflets, m. p. S4--85';
(3) when heated
with alcoholic potassium hydroxide and chloroacetamide, it yields
thiodigZycoZlamidephenylhydrazide,

NH,*CO*CH,*S-CH,*CO*N*NHPh,
colourless leaflets, m. p. 135-136" ; (4) with alcoholic potassium
hydroxide and ethyl chlorocarbonate it yields cccrboxytlbioglycollphenylhydr~xicle,CO2H*SoCH,*CO*NH*NHPh,
m. p. 156-157';
thepotassium
salt has m. p. 212-213'.
The following substances are prepared by methods similar t o
those just described ; pJ~enyZmethylJiydraxinethiocyanoacetat~,m. p.
; carbaminetJ~ioglycotZpJienylmethyZh?/draxide, C,oH1,O,N,S,
65-68'
m. p. 145-146' ; nzethyZthiogZ?/coZZphen~Z~~thylhydraxide,
C1,H,,ON,S,
needles, m. p. 74-75O ; carbethoxytJiiogZycoZ2pJLenylme2hylhgdraxide7
Cl,Hl,O,N,S, colourless leaflets, m. p. S2 -S3O ; carbanzinethioglycoll-ptolylhydrazide, Cl0Hl3O2N3S, m. p. 164-1 65' ; thioglycoll-p-tolylhyJraxide, CgH,,ON,S, m. p. 125-1 26' ; dithiodigZycoZZ-p-toZyl~~~rcmide, ClsH,t202N,S,, glistening leaflets, m. p, 182-183';
rnethyltiiiogZycoZGptoZylhydraxicEa,C,,H1,ON,S, glistening leaflets, m. p, 108-1 09';
thiodigZycoZZumide-p-toZyZh?/draxide,
C,,H,,O,N,S, glistening, pale yellow
W. H. G.
needles, m. p. 148-149".
C a s e of Isomerism. [Acylazoaryl Compounds.] GIAcoicro
PONZIO
(Gaxzettu, 1909, 39, ii, 535-546).-The
author has carried
out further investigations on the yellow, white, and red isomerides,
Cl,H,004N,, obtained by the action of benzenediazonium acetate on
the potassium derivative of o-dinitrotoluene (Abstr., 1908, i, 482,
582; 1909, i, 443, 681). The results obtained settle definitely the
structure of the red isomeride, and render probable the accuracy of
that already assigned to the white compound, but do not admit
of the structure of the yellow derivative being determined.
For the yellow compound, the author has suggested the formula
NO,*CPh(NO)0O-N: NPh, which would explain its isomeric change
into a-nitro-/3-nitroso-a-benzoyl-~-phenylhydrazine
(Abstr., 1908, I,
482). On the basis of this formula, Dimroth and Hartmann (Abstr.,
1909, i, 66) indicate a n amalogy between this yellow compound and
benzene-0-azotribenzoylmethane, obtained by the interaction of the
potassium derivative of tribenzoylmethane with benzenediazonium
acetate, and suggest that the yellow compound is a true 0-azoderivative and not a diazo-derivative. But, apart from the fact that
the properties oE Dimroth and Hartmann's compound are explained
equally well by regarding it as a true diazonium salt (compare
Auwers, Abstr., 1909, i, 67), its analogy to the author's yellow
compound is not borne out by its behaviour with ethereal hydrochloric acid. Thus, benzene-0-azotribenzoyImethane gives benzenediazonium chloride and tribenzoylmethane, whilst the diazobenzene

ORGANIC CHEMLSTRY.

i. 193

derivative of o-dinitrotoluene gives the isomeric compounds, a-nitroP-nitroso-a-benzoyl-/I-phenylhydrazineand o-nitrobenzaldehyde-pnitrophenylhydrazone, NO2*CPh:N*NH*C,H,*N0,, treatment with
water converting the former of these isomerides into p-nitroso-abenzoyl-P-phenylhydrazineand leaving the latter unchanged. The
formula NO,*CPh(NO)*N:NPh for the yellow compound (uide
supra) does not, however, explain its reaction with alcohol, with
formation of w-dinitrotoluene, nitrogen, acetaldehyde, and benzene.
The reactions of the red isomeride are not in accord with the structure, NPh:N*CPh(N0,)2, originally assigned to it (Abstr., 1908,
i, 482). Thus, on reduction by means of tin and hydrochloric acid, it
yields ammonia, benzoic acid, and p-phenylenediamine. By sodium
methoxide it is converted in to a-dinitrot etraphenyltetrazoline (compare Bamberger and Grob, Abstr., 1901, i, 296). These results indicate that the red compound is r o t o-benzeneazo-w-dinitrotoluene, but
w-nitrobenzaldehyde-p-nitrophenylhydrazone
(compare Bamberger and
Grob, Abstr., 1901, i, 567), and direct comparison confirms this indication. The isomeric change of the yellow compound into o-nitrobenzaldehyde-p-nitrophenylhydrazoneconsists in the passage of a
nitro-group from a n aliphatic carbon atom into the para-position of
the benzene nucleus, and such a transformation is best explained by
regarding the yellow compound as w-benzeneazo-w-dinitrotoluenp,
NPh: N*CPh(NO,),.
It follows from these results that the compound, m. p. 130-135',
previously described as w-dinitro-w-benzeneazo-p-xylene,
must be
regarded as w-nitro-ptolualdehyde-p-nitrophenylhydrazone,
N 02*C6H,*NH*N:
C(N0,) C,H,Me,
and that described as o-dinitro-w-benzeneazo-p-methoxytoluene,
m. p.
141-1 48O, as o-nitroanisaldehyde-p-nitrophenylhydrazone,
N02*C6H;NH*N:C( N0,)-C,H4*UMe.
But, in addition to the diazobenzene derivatives of the primary
dinitrohydrocarbons, the ortho-substituted diazo-salts are also transformed into red isomerides when dissolved in moist ether, and i n this
case, too, there takes place transference of a nitro-group from the
aliphatic carbon atom to the para-position of the benzene nucleus.
So that the compound, m. p. 137' (decomp.), previously described
must be re(Abstr., 1909, i, 443) as w-o-tolueneazo-w-dinitrotoluene
garded as w-nitrobenzaldehyde-p-nitro-o-tolylhydrazone,
NO,* C,H,Me*NH*N:CPh*NO,,
a structure which is confirmed by the fact that it yields benzoic acid,
ammonia, and 2 :5-diaminotoluene on reduction with tin and hydrochloric acid ; this compound may also be obtained by the interaction of
the sodium derivative of o-nitrotoluene and m-nitro-o-toluenediazonium
sulphate : CHPh:NO,Na + NO,-C,H,Me*N,*HSO, = NaHSO, +
NO,*C,H,Me*NH-N:UPh*NO,. Further, the compounds described as
o-o-chlorobenzeneazo-o-dinitrotoluene,
m. p. 140' (decomp.), and o-obromobenzeneazo-w-dinitrotoluene, m. p. 140' (decomp.) (hbstr.,
1909, i, 443), must be regarded as the o-chloro-p-nitrophenylhydrazone
and o-bromo-p-nitrophenylhydrazone respectively of o-nitrobenzaldehyde, NO,*C,H,Cl-NH*N:CPh*NO, and
N0,*C6H,Br*NH*N
:CPh*NO,.

i. 194

ABSTRACTS OF CHEMICAL PAPERS.

These results explain the observation that, whilst the orthosubstituted diazonium salts give with moist ether their red
isomerides, that is, the corresponding ortho-substituted p-nitrohydrazones, para-substituted diazonium salts, under the same conditions, lose two atoms of nitrogen and three of oxygen i n the form
of nitrous compounds, giving acylazoaryl derivatives, the isomeric
acylarylnitronitrosohydrazines being formed as intermediate products :
R*C(N,O,)*N,Ar --+R*C0*N(NO2)*NAr*NO
-+ R*CO*N:NAr;the
para-position which the nitro-group tends to assume is in these cases
occupied. It isafound, indeed, that these compounds, by the action of
absolute alcohol in the cold, give small yields of red isomerides, the
nitro-group entering the benzene nucleus in the ortho-position. The
red isomeride, m. p. 153-154" (decomp.), of the p-diazotoluene derivative of o-dinitrotoluene (Abstr., 1909, i, 443) is found to be, no6
w-p-tolueneazo-w-dinitrotoluene, but o-nitrobenzaldehyde-o-nitro-ptolylhydrazoue, NO,-C,H,Me*NH*N :CPh-NO, ; reduction of this
compound (which may also be obtained by the interaction of the
sodium derivative of w-nitrotoluene and m-nitro-p-toluenediazonium
sulphate : CHPh:N02Na + N0,*C,H,Me*N2*HS0, = NaHSO, +
NO,*C,H,Me-NH*N :CPh-NO,) with tin and hydrochloric acid
gives benzoic acid, ammonia, and 3 : 4-diaminctoluene. Similarly, the
compound described as o-p-chlorobenzeneazow-dinitrotoluene (Abstr.,
1909, i, 443), m. p. 161" (decomp.), must be regarded as o-nitrobenzaldehyde-p-chloro-o-nitrophenylh
ydrazone,
NO, C,H,Cl*NH*N: CPh*NO,,
and that described as o-p-bromobenzeneazo-o-dinitrotoluene as
w-nitro benzaldeh y de-p-bromo-o-nitropheny 1hydrazone,
N0,*C,H3Br*NH*N:CPh*NO,.
That the white isomeride, best obtained by dissolving the diazobenzene derivative of o-dinitrotoluene in anhydrous benzene, is
a-nitro-/3-nitroso-a-benzoyl-~-phenylhydrazine,
N02*NBz*NPh*N0,is
confirmed by its transformation into benzoylazobenzene, NBzzNPh
T. H. P.
(Abstr., 1909, i, 681).

Passage of the Nitro-group from an Aliphatic Carbon Atom

t o the Benzene Nucleus. GIACOMOPONZIO
and R. GIOVETTI
(Gazxettcc, 1909, 30,ii, 546-556).-The
action of the sodium derivative of o-isonitrophenylacetonitrile on benzenediazonium acetate yields
benzeneazo-w-nitropheny lacetonitrile, NO,*CPh( CN) N: NPh, which,
by the passage of the nitro-group to the para-position of the benzene
nucleus, undergoes spontaneous transformation into o-cyanobenzaldehyde-p-nitrophenylhydrazone,
,CN*CPh:N,N*C,H,*NO,, and a small
proportion of the corresponding o-nitrophenylhydrazone. This transformation, which is similar to that observed with the diazobenzene
derivative of o-dinitrotoluene (compare preceding abstract), also
takes place with substituted diazo-derivatives, the nitro-group entering
the benzene nucleus in the ortho-position in cases where the paraposition is occupied. The initial compounds formed from o-nitrophenylacetonitrile are, however, less stable than those yielded by
w-dinitrotoluene, and undergo isomeric change so rapidly that they

ORGANIC CHEMISTRY.

i. 195

cannot be obtained in the dry state. Still more unstable are the
compounds formed by o-nitrotoluene with diazonium-salts, this reaction
always giving w-nifrobenzaldehydephenylhydrazones. I n the latter
case, it is a hydrogen atom from the aliphatic carbon atom which
converts the group *N:N* into :N*NH-,whilst in the previous cases
i t is the hydrogen atom from the para- (or ortho-) position of the
benzene nucleus.
Be?txsneaxo-o-nitrophenykccetonitrile,NO,*C Ph(CN)=N:NPh, forms
a pale yellow, flocculent precipitate.
w-Cyanobenxaldehyde- p-nitrophenpZhydrazone,

CN*CPh:N*NH*C6H,*N0,,
crystallises in yellow plates, m. p. 208--209O, dissolves in alkali
hydroxides, forming intensely violet solutions, and, on reduction by
means of tin and hydrochloric acid, yields benzoic and hydrocyanic
acids and p-phenylenediamine.
o-Cyanobenzaldehyde-o-nitrophenylhydraxone, C10H1402N4, crystallises in orange-red, flattened needles, m. p. 1 8 7 O , gives a reddish-brown
coloration when dissolved in alkali hydroxide solution, and yields
benzoic and hydrocyanic acids and o-phenylenediamine when reduced
with tin and hydrochloric acid.
o-Cyanobenxaldehyde-p-nitro-o-tolylhydraxone,
CN*CPh:N*NH*CGH,Me*NO,,
obtained by the isomeric change of o-tolueneazo-o-nitrophenylacetonitrile (prepared by the interaction of the sodium derivative of isonitrophen y lacet onitrile and 0-toluenediazonium acetat e), cry stallises from
benzene in brownish-yellow needles, m. p. 188', forms intensely
violet solutions with alkali hydroxide, and yields benzoic and hydrocyanic acids and 2 :5-tolylenediamine on reduction.
o-Cyanobenxaldehyde-o-nitrop-tolylhydraxone,
CN*CPh:N*NH*C,H,Me*NO,,
formed by the isomeric transformation of p-tolueneazonitrophenylacetonitrile, crystallises in orange-red needles, m. p. 160, gives a winered coloration with alkali hydroxides, and yields benzoic and hydrocyanic acids and 3 : 4-tolylenediamine on reduction.
o-Cyanobenxaldehyde-ochloro-p-nitrophe?iyZhydraxone,
CN*CPh:N*NH*C6H,C1*N02,
prepared from o-chlorobenzenediazonium acetate and the sodium
derivative of o-isonitrophenylacetonitrile, forms orange-coloured
needles, m. p. 1 8 2 O , and gives violet-red solutions with alkali
hydroxides.
o-Cy~nobenxaldehyde-p-chloro-o-nitrophenyl~ydraxone,formed from
p-chlorobenzeneazonitrophenylacetonitrile by isomeric change, crystallises in brownish-yellow laminx?, m. p. 240, and gives intensely violet
solutions with alkali hydroxides in presence of a small quantity of
alcohol.
o.Cyanobenxaldehyde-o ; p-dinitpophenylhydraxone,
CN*CPh:N*NH*C,H,( NO,),,
formed by isomeric change of either 0- or p-nitrobenzeneazonitrophenylacetonitrile, crystallises in reddish-brown prisms, m. p. 246' (decomp.),
and gives intensely violet solutions with alkali hydroxide in presence
T. H. P.
of a drop oE alcohol.

i. 196

ABSTRACTS OF CEEMICAL PAPERS.

Limiting Cases between Polymorphism and Isomerism.

ROBERTO
CIUSAand MAURICEPADOA
(Atti R. Accad. Lincei, 1909, [v],
18, ii, 621-626).-m-Nitrobenzaldehydephenylmethylhydrazone
forms
two modifications, one red and the other yellow, both having m. p.
120-125' (Labhardt and Zembruski, Abstr., 1900, i, 125, found 112",
and Bamberger and Pemsel, Abstr., 1903, i, 286,112-113'),
at which
temperature mixtures of the two also melt. The yellow form has t h e
normal molecular weight in freezing benzene, the solution depositing
the red modification on evaporation. Certain solvents, such a s
chloroform and benzene, convert the yellow into the red form, which
may also be obtained by strongly cooling solutions of the yellow
modification, or by seeding a n alcoholic solution of either form with
the red crystals. The red modification passes into the yellow
on boiling with alcohol or ethyl acetate, on seeding its alcoholic solution with a yellow crystal, or on prolonged immersion in water or
alcohol. There is no apparent or spectroscopic difference between
solutions of the two products even when these are freshly dissolved.
Both forms give with picryl chloride one and the same additive
compound, which undergoes a considerable amount of dissociation even
in concentrated alcoholic solution, giving the red h'ydrazone.
p-Nitrobenzaldehydephenylmethylhydrazone also occurs in two
forms, one red and the other yellow, both having m. p. 130' (Labhardt
and Zembruski, Zoc. cit., found 132'). I n this case, too, each form
can be transformed into the other, but the change in colour is less
distinct than with the meta-isomeride, and the red modification is
very unstable unless stored under special conditions.
o-Nitrobenzaldehydephenylmethylhydrazone occurs only in a red form, m. p. 90'
(Labhardt and Zembruski, Zoc. cit., found 77"), but m-nitroanisaldehydep-nitropheny lhydraxone, which is yellow when perfectly dry, becomes
red immediately in moist air (Abstr., 1907, i, 137).
The criteria given by Wegscheider (Abstr., 1902, ii, 126) are
insufficient to indicate whether this phenomenon is a case of isomerism
or one of polymorphism. I n this and i n other cases, the phenomena
of polymorphism and of isomerism approach so closely t h a t the existence of a line of demarcation is not evident, (compare Fock, this vol.,
ii, 23).
T. H. P.

Pantachromism of Dimethyl- and Diphenyl-violurates.

ARTHUR
HANTZSCH
and ROBERT
ROBISON
(Ber., 1910, 43, 45-68.
Compare Abstr., 1909, i, 331, 333, 335).-In addition to the yellow
lithium dimethylviolurate (Zoc. cit., i, 335), a red salt, C6H60,N,Li, has
been prepared. It yields carmine-red compounds with lEtOH and
1H,O. The yellow salt becomes red i n the presence of traces of water.
The solutions of the two lithium salts i n pyridine are red, and i n phenol,
orange-coloured . A yellow compound with phenol, C,H,O,N,Li,PhOH,
is described ; i t loses phenol when exposed to the air, and forms the red
hydrated salt.
When the violet sodium salt is exposed to the air, it absorbs
moisture (I mol.) and becomes red. A red anhydrous sodium salt can
be prepared by heating the compound containing ethyl alcohol, The

ORGANIC CHEMISTRY.

i. 197

compound with phenol (1PhOH) is yellow, and when heated at looo

with methyl alcohol yields the anhydrous red salt. The blue potassium
salt when exposed to the atmosphere yields the violet hydrate ($H,O) ;
the corresponding phenol compound has a rose-red colour.
The bluish-violet rubidium salt (loc. cit., 334) contains 0*5H20,and
when boiled with methyl alcohol yields a pure b l w anhydrous salt ; the
phenol compound has a rose-red colour. The caesium salt crystallises
from alcohol in deep indigo-blue needles, and yields a rose-red phenoxide.
Dimethylvioluric acid and phenol yield a yellow additive compound.
have been
Two coloured silver pyridine salts, C,H,O,N,Ag,C,NH,,
prepared : a labile green salt by the addition of ether to the pyridine
solution of brown silver dimethylviolurate, and a stable 6ZuislmioZet
salt obtained when the green salt is left in contact with ether and
pyridine.
The methylamine salt, C,H70,N3,NH,Me, has a rose-red colour, and
when exposed to the air yields the yellow acid salt ;the dimethylamine
salt is violet, the normal trimethylamine salt is blue, the acid salt
orange-yello w, and the tetramethykaminoszium salt is blue. The sthylamine salts are very similar, The normal tripropylamine salt could
not be isolated; the acid salt, 2C6H7O4N3,NPr3,
is orange-yellow. The
dibenxylamine salt exists in a labile red and a stable bluish-violet
modification. Piperidine yields a stable blue and a labile red salt,
Pyridiizs yields a stable yellow acid salt.
C,H70,N,,C,H,,N.
Diphenylvioluric acid was prepared by a modification of Whiteleys
method (Trans., 1907, 91, 1330); the pure neutral salts are best
prepared in alcoholic solution, as they readily decompose in the
presence of aqueous alkalis. They crystallise with alcohol, which can
be completely removed by heating the very finely divided salt. The
lithium and sodium salts exist in labile red and stable yellow modifications, and yield red compounds with 1EtOH. The ammonium
salt forms a violet compound with EtOH. The normal potassium,
rubidium, and caesium salts are blue, and the acid ru6idium and
caesium salts green ; the magnesium and xirzc salts are yellow ; the
thallous silver saits exist in stable green and labile colourless forms.
The acid silver salt, C3,H2,0,N,Ag,3H,0,
has a n orange colour.
The salts of dimethyl- and diphenyl-violuric acids exhibit both pantachromism and chromotropism. The labile forms of the salts are
usually stable when perfectly dry, but pass readily into the more
stable forms in the presence of a little water or alcohol. An
increase in the depth of colour of the salts is observed as the
metallic radicle becomes more positive, and in the case of substituted
ammoFium salts a n increase in depth of colour is observed with an
increase in the number of alkyl groups, The addition of phenol to
the molecule of the alkali salts results in a diminution of colour,
whereas the addition of pyridine produces a n increase in colour,
except in the case of the compound of silver violurate and pyridine,
which is colourless, and to which the formula
is ascribed.
An increase in the depth of colour with a n increase in the positive
VOL. XCVIII. i.
P

i. 198

ABSTRACTS OF CHEMICAL PAPERS.

nature of the metallic radicle is noticed in the case of concentrated

aqueous or alcoholic solutions, and also of solutions in non-ionising
solvents, such as chloroform or phenol. A negative solvent tends t o
lessen the depth of colour of the solution of any given salt.
Molecular-weight determinations in phenol and ethyl acetate indicate
that the .different coloured isomeric salts are unimolecular.
The absorption spectra solutions of the acids and of their alkali salts
have been measured.
A comparison of the absorption curves for diphenylvioluric acid, its
lithium and cmium salts, and nitrosoisopropylacetone (Baly and Desch)
points to the conclusion that the blue violurates should be represented
as nitroso-enolic salts: CO\NR.(COMe)
"R*CO >
-CN
. *.
The violuric acids as true oximino-keiones are the more completely
transformed into the structurally isomeric nitroso-enols the more
positive the nature of the metallic radicle present and the solvent.

J. J. S.
Pantachromic Salts of Oximino - oxaeolones. ARTHUR
HANTZSCH
and J. HEILBRON
(Bey., 1910, 43, 68-82.
Compare
Hantzsch and Eemmerich, Abstr., 1909, i, 336).-pBromoand
p-methoxy-derivatives of oximinophenyloxazolone yield pantachromic
salts with colourless bases. The esters and acyl derivatives on the
other hand are only pale yellow. The salts of the bromo-derivative
are comparatively stable, and dissolve in various neutral solvents.
Molecular-weight estimations in acetone, pyridine, and chloroform
indicate t h a t the salts, botlh ammonium and metallic, are unimolecular
in solution. The colours of the salt solutions in non-ionising media
increase in depth with the positive nature of the metallic radicle
present.
The abeorption spectra, both visible and ultra-violet, of the
oxazolones and their salts in different solvents have been tabulated.
The free acids are true oximino-compounds, and their absorption
spectra resemble those of their ethers and acyl derivatives. The
phenolic solution of the oximino-compound is distinctly yellow. The
ultra-violet spectra of the salts do not differ materially from those of
the free acids, but the visible spectra of the salts show characteristic
absorption bands which are not present in the spectra of the free acids.
The blue solutions of the potassium, rubidium, caesium, and tetraalkylammonium salts give practically identical spectra. The conclusion
is drawn that the yellow salts derived from feeble bases possess the
true oximino-ketone structure, whereas the blue salts derived- from
strong bases have a nitroso-enolic structure.
p-BromophenyZoxazoZone,prepared from ethyl p-bromobenzoylacetate
and hydroxylamine, crystallises in glistening plates, m. p. 1 1 8 O
(decomp.), and reacts with nitrous acid, yielding oxirnino-p-bvomophenyloxazolone,

N-

C,H,Br*C<c(:N.OH).

pale yellow monohydrate.

bo, which

crystallises as a

The anhydrous compound has a pure

i. 199

ORGANIC CHEMISTRY.

yellow colour and decomposes at 166'. The salts readilydecompose in

aqueous alkaline solutions, but are stable in alcoholic solution. The
lithium salt, C9H40,N2BrLi, exists in a stable yellow form only; the
sodium salt forms orange-red needles, which form a pale rose-coloured
monohydrate. The potassium salt exists in a rose-red and a reddish-violet
form, and forms a pale red phenol compound, CgH403N2BrK,C,H,*OH.
The acidpotassiunz salt is yellow. Rose, blue, and violet rubidium salts
have been prepared ; the mid salt is golden-yetlow, and the phenol
compound, pale red. Rose-coloured and bluish-violet caesium salts,
together with pale red phenol compound, are described. The barium
salt, (C,H403N2Br)2Ba,4H20,is red, but when dehydrated is orangecoloured. Similar calcium and mapesium salts have heen obtained.
The zinc salt, (C9H,O3N2Br),Zn, is pale yellow, the lead salt pale rose,
and the thallium salt flesh-coloured. A blue, a n orange, and - a Jleshcoloured silver salt have been prepared, and a carmine-red monohydrate ;
the orange and the blue salts yield the same methyl ether. The silver
salts are insoluble in neutral media, but dissolve in pyridine, yielding
dichromatic solutions. The following additive compounds are described :
C9H40,N2BrAg,2C,H,N, violet ; C,H,03N,BrAg, 2NH,, deep blue j
C6H,0,N2BrAg,NH3, rose ; CgH403N,BrAg,CH,CN, carmine-red.
The anmonium salt is orange-coloured ; the methylamine, ethylamine,
pi-opylamine, and benzylamine salts are rose-coloured ; the dimethylamine and diethylamine salts a r e salmon-red ; the dipropylamine salt,
orange-coloured ; the dibenxylamine salt, red ; the trimethylamine salt,
violet ; the triethylamine salt, bluish-violet ; the tripropylamine salt is
red, and the quaternary ammonium salts crystallise in deep blue plates
and their solutions resemble those of the alkali salts. The normal
pyridine and picoline salts are pale yellow. The ntethyl ether,
C( :No OMe) *YO
C6H4BK" c<

N-

0 '

forms pale yellow crystals, m. p. 129" (decomp.). The acetyl derivative

also forms yellow crystals, m. p. 161' (decomp.), and the benzoyl
derivative decomposes at 167'.
CH *CO
Anisyloxmolone,
, forms crystals with a

OMe-C,H,*C<.Ll,

satiny lustre, and m. p. 140 -141" (decomp.). The oximino-derivative,

O M C Y C , H ~ < ~ ( forms
: ~ ~ a~ yellow
) ~ ~ monohydrate
~
;the anhydrous
compound has a deeper yellow colour,and decomposes a t 149'. The
salts are not so polychromatic as those of the corresponding bromine
derivatives
The following salts are described : Sodium, C1,?3704N2Na, orangered ; potassium, reddish-purple needles ; caeszum, bluish-violet ;
ammonium, red ; silve~, labile rose-coloured and stable blue ;
Cl,,Hv04N2Ag,
2NH3, red. The methyl ether, C,,Hl,0,N2, crystallises in pale yellow needles, m. p. 126O, and when hydrolysed
C(C0,H):N
yields anisylficraxancarbozylic acid, OMe*C,H,-C<
m- P.
N-----

A,

99-100'.

This acid is undoubtedly formed by the addition of water

P2

i. 200

ABSTRACTS OF CHEMICAL PAPERS.

and the opening of the oxazolone ring, and the subsequent elimination
J. J. 8.
of methyl alcohol.

Pantachromism of Violurates and Salts of Analogous

Oximino-ketones. ARTHUR
HANTZSCH
(Ber., 1910,43, 82-91).The following general conclusions are given : (1) all polychromatic
salts are unimolecular i n solution, pointing t o the isomerism and not
polymerism of different coloured salts derived from the same metal ;
(2) the solutions pass from yellow or orange through red and violet to
blue as the positive nature of the metallic radicle increases ; (3) the
absorption curves of yellow solutions are somewhat analogous t o the
curves for solutions of the free oximino-ketones in indifferent solvents
and to solutions of their acyl and methyl derivatives. Deep blue
solutions, on the other hand, show distinct selective absorption, and
are optically closely related t o blue aliphatic nitroso-compounds. The
change in colour is attributed to a chemical change, namely, to t h e
passage from the oximino-ketone form to t h e nitroso-enolic form :

-+ OH*Y:Q.NO.
~ l solutions
l
of the salts consist of an equilibrated mixture of the
two forms, the proportions of each depending on the positive character
of the metallic or substituted ammonium radicle present, and also on
the nature of the solvent. It is shown t h a t a mixture of the yellow
acetone solution of zinc diphenyl0
0
violurate with the blue acetone solu-@..,&f
tion of potassium diphenylviolurate
I
I,
is red and not green.
I
Leuco-salts yield yellow solutions,
indicating a partial conversion into
-c\/O
-'\do
N
(1.1
N
the nitroso-enolic form. The solid
salts of orange, red, or purple colour
0
0
are also regarded as mixed crystals
of the two isomeric salts.
/\/\BI
/\/'.-.,M
When a salt exists in a yellow
and
I and a blue form, these are regarded
as isomeric in the sense of Werner's
\/\yo
NO
valency-isomerism (for example, I).
NO
(11.)
Similarly, the yellow and red salts
of nitrophenol are represented as (11)
The red aci-ethers are regarded as analogous to the red salts.
J. *J.S.

O:Q*$XN*OH

1 1

1 I

\/\/*

Purpuric Acid. ARTHUEHANTZSCH

and ROBERTH,OBISON
(Be?*., 1910, 43, 92--95).-The
formula of Piloty and Slimmer
and Stieglitz (Abstr., 1904, i, 634) for purpuric alid is analogous
t o t h a t of

the

blue

violuratee:

*<NH
NHpCo>C*NO
C(OH)

and

It has not been found possible to prepare coloured ethers or

to isolate the pure violuric acid. A method is recommended for the
preparation of pure murexide (ammonium purpurate) (compare

ORGANIC CHEMISTRY.

i. 201

Hartley, Trans., 1905, 87, 1981). The values for the electrical
= 5 1-8,
conductivity of the pure salt are : p25s= 51-2, pb12= 5 1.5, p,024
and pOc= 52.9. The conductivity of the system : rnurexide + HC1=
The purpuric
purpuric acid+NH,Cl has been determined a t 0'.
acid is only slowly transformed into uranil and alloxan, and becomes
colourless after three days. The initial value for p512is 225, but this
gradually falls to 167 after twenty-five minutes, and to 21 after
three days.
The value ps for purpuric acid at OOhas been found to be 248.8
from the equation pOcHCl- paCNH4Cl-I-paCmurexide = pZ purpuric
278.8
82.9
52.9
248-8
acid. The degree of dissociation at 0" and vSJ2is thus 0.9, and K = 0.0158.
Alloxan is not regarded a s a quinonoid substance, since it shows
J. J. S.
only general absorption.

Synthesis of 5 :7 :5':7'-Tetrachloroindigotin. ERWIN

OBERREIT
(Compt. rend., 1910, 150, 282-283.
Compare Danaila, this vol., i,
137).-The constitution of this substance follows from the fact that it
may be prepared from dichloroglgcine-o-carboxylicacid which has
been obtained from 3 : 5-dichloroanthranilic acid.
w. 0. w.
VONGERICHTEN
and L. KRANTZ
(Ber.,
Quinoline-Red. EDUARD
1910, 43, 128-130).--&uinoline-red
is obtained by the interaction of
molecular proportions of benzotrichloride, quinaldine, and !isoquinoline
in presence of zinc chloride (Hofmann, Abstr., 1887, 380). When
oxidised with potassium dichromate, a base is formed, m. p. 125O,
which is regarded as quinolyl isoquinolyl ketone, C,H,N*CO*C,H,N,
since on heating it with concentrated potassium hydroxide, isoquinoline
and a n acid, probably quinaidinic acid, are formed. The base dissolves
with a yellow coloration in concentrated acids, and yields a n intensely
yellow-coloured, crystalline precipitate with phosphorus pentachloride
in chloroform solution. The oxime forms somewhat grey-coloured,
glistening plates, m. p. 245'. A second product of the oxidation is
benzaldehyde.
E. I?. A.
Acenaphthem Series. FRITZ ULLYANN
and ERWINCASSIRER
(Bey., 19 10, 43,439--445).-As
acenaphthene is now a commercial
product, the authors have attempted to convert it into dyes o r into
products from which dyes may be obtained.
A 407; yield of nayhthalic acid can be obtained by oxidising
acenaphthene with sodium dichromate and sulphuric acid (compare
Graebe and Gfeller, Abstr., 1892, 863). Naphthastyril (Ekstrand,
Abstr., 1886, 715; 1889, 52) is formed when naphthalimide is
treated with sodium hydroxide solution and then with sodium hypo
chlorite at 15-25'.
It reacts with 10% sodium hydroxide solution
and p-toluenesulphonic chloride, yielding 8-p-toluenesulphonykaminonaphthoic acid, C7H7*S0,*NH*CI,H,*C0,H, as colourless needles,
m. p. 158-159O (decomp.). With acetic anhydride the acid yields
p-toluenesulphonylnaphthastyril,Cl,H1,O,NS, as straw-yellow,glistening
needles, m. p. 174'.

i. 202

ABSTRACTS OF CHEMICAL PAPERS.

Phenylacenaphthaphenazonium nitrate (annexed formula), obtained

from acenaphthenequinone, a-aminodiphenylamine, and acetic and
nitric acids, crystallises in glistening, yellow
needles. It dyes cotton mordanted with
/-\-c.N-tannin"a pale lemon-yellow, The xincochloride,
11 I
2C2,HI,N,ZnC13, forms yellow plates with a
/ \ C*NPh
brassy lustre ;the dichromate,
\-/- I
2(' 4H15N2)2Cr207,
NO3
forms a yellowish-brown, crystalline powder,
and the free base, C2,H,5N2*OH,
a yellowishforms glistening,
green precipitate. The nzethyl ether, C,,H,,ON,,
yellow crystals, m. p. 180-185.
3-Chlorophenylnaphthaphenaxoniumnitrate,

'-' )C,H,

a/

obtained from acenaphthenequinone and 5-chloro-2-aminodiphenylamine, forms yellow needles, and dyes cotton mordanted with tannin a
yellowish-green. The methyl ether, C,,H170N2CL, forms pale green,
glistening plates, arid has rn. p. 200-220.
2-A minopheny I -acenuphthaphenaxonium chloride,
crystallises in deep violet-coloured needles, and dyes mordanted
cotton Bordeaux-red. The nitrate,
C,4H,,0,N,,
crystallises in violet
plates. The acetyl derivative,
C26H1,0N3C1,

crystallises in long, red needles.

N
Acenaphthaphenaximaxim (annexed
formula), obtained by condensing
acenapht henequinone and 2 :3-diaminophenazine in acetic acid solution,
crystallises in red needles, which are not molten at 320'.

J. J. S.
Methylene-Blue. PAULLANDAUER
and HUGOWEIL (Ber., 1910,
43, 198-203).-Durr~chnabel
has shown (Digs., Giessen, 1907) that
indamines, oxazines, thiazines, and other para-quinonoid substances
are converted by sulphurous acid o r hydrogen sulphite into
sulphonated leuco-compounds, whilst ortho-quinonoid substances, such
as the indulines and safranines, are not reduced, and usually form
sparingly soluble sulphites. The authors find that phenylhydrazine
acts in a similar way. Methylene-blue, suspended in alcohol, is
treated with phenylhydrazine a t the ordinary temperature ; after
half a n hour's warming on the water-bath, the system is allowed to
cool in carbon dioxide or coal gas. Nitrogen is evolved, and leucomethylene-blue, m. p. 185', is obtained in yellow needles. The leucocompound is stable in dry oxygen, and in the presence of alkaline
oxidising agents can be directly acetylated by acetic anhydride, and
yields a yellow sodium salt with alcoholic sodium ethoxide. Methg lenegreen by similar treatment yields brown needles of nitroleucomethyleneblW, C16Hla02N4S, m. p. 146-14'7'.
c. s.

ORGANIC CHEMISTRY.

i. 203

Synthesis of Hetero-condensed, Heterocyclic Compounds

with Two Nuclei. Derivatives of 2-Methyl-1:3.triaeo-'7:0'pyrimidine [%Methyl-1:3 :7 : 9-benztetrazole] from 5-Amino2-methyl-1: 3 :4-triazole. CARLBULOW
and KARL
HAAS
(Ber., 1910,
43, 375-381.
Compare Abstr., 1909, i, 614, 615 (and Errata), 1470;
this vol., i, 80, 81).-5-Amino-2-methyl-l : 3 : 4-triazole contains a
labile hydrogen atom attached to the nitrogen next the basic group.
Accordingly, it interacts with 1 : 3-diketones, forming di- and trialphyl or aryl derivatives of 2-methyl-1 :3 : 7 : 9-benztetrazole, or with
keto-esters, forming methyl benztetrazolehydroxylic acid derivatives.
yXe=N*Q :N
2 ; 4 : 6 - Trimethyl - 1 : 3 : 7 : 9 - benxtetraxole,
CH: C3le.N *N>CMe,
prepared by interaction of the aminotriazole with acetylacetone, forms
colourless needles,. m. p.
- 141-142'.
QMe==N*T :N
2 ; 4 :5 : 6-Tetramethyl-1 : 3 : 7 :9-benxtetraxole,
CMe: CMe'lU *N>CMe,
obtained in a similar manner from methylacetylacetone, has m. p.
116-1 17".
4-Phenyl-2 : 6-dimethyl-1 : 3 : 7 : 9-benxtetq*azoleforms colourless, radially grouped, long, thin prisms, m. p. 110-1 1 lo.
4-&drox.~-2 : 6-dimethql-1 : 3 :7 :9-benztetrccxole,
obtained by boiling aminornethyitriazole with ethyl acetoacetate i n
glacial acetic acid solution, separates in glistening crystals, m. p. above
880'.
This and the following compounds are acidic, forming salts with
alkalis. These react neutral in aqueous solution, and give amorphous
or crystalline precipitates with salts of the heavy or alkaline-earth
metals. Thus the lead salt forms short plates; the copper salt, bright
preen needles ;the zinc salt, stellar aggregates of needles ; the calcium
salt, glistening needles.
4- Hydroxy-2 :6-dimethyl-5-ethyl-1 : 3 : 7 :9-benxtetraxole,prepared from
ethyl ethylacetoacetate, has m. p. 262O, and forms soluble neutral salts,
which are not decomposed by carbon dioxide,
4-Hydroxy-6phenyZ-2-methyl-1
: 3 : 7 : 9-benztetvazole, obtained from
ethyl benzoylacetate, forms long, colourless needles, which do not
E. F. A.
melt a t 293O.

Yellow and Red Forms of Salts and Hydrates of Hydroxyazo-derivatives. ARTHUR

HANTZSCH
and PHILIP
W. ROBERTSON
(Ber.,
1910, 43, 106-122.
Compare Tuck, Trans., 1907, 91, 460; Gorke,
Koppe, and Staiger, Abstr., 1908, i, 477).-The salts of hydroxy-azocompounds appear to exist in' yellow and red modifications similar to
the yellow and red salts of nitrophenols. It is only in the case of
silver salts t h a t yellow and red isomeric salts have been obtained
from the same compound. Salts of the type R*N,*C,H,*OM+
0.5MeOH (EtOH, CH,*CO,Et, COMe,, or C,H,N) are common ;they are
orange-coloured, and are regarded as compounds of 1 mol. of red salt,
1 mol. of yellow salt, and 1 mol. of the crystallising medium. When
the last is removed, they yield red or yellow salts, or, sometimes, orangecoloured salts.

i. 204

ABSTRACTS OF CHEMICAL PAPERS.

The following table gives the colours of the salts of four hydroxyazocompounds :

H .........
Li ......
N a ......
K .........
R b ......
Cs ......
Ag

...... {

Benzenep-Chlorobenzene- p-Bromobenzeneazophenol.
azophenol.
azophenol.
Yellow
Yellow
Yellow
Pale yellow
Pale yellow
Pale yellow
Orange
Orange
Orange
Red
Red
Pale red
Red
Orange
Dark red
Red
Red
Pale red
Yellow (stable) Yellow (stable) Yellow (stable)
Red (labile)
Red (labile)
Red (labile)

Benzeneazo-o-dibromophenol.
Orange
Pale yellow
Yellow
Orange
Orange
Orange
Red

It is noticeable that the lithium salts are paler in colour than the
original hydroxy-derivatives, and that, as a rule, the caesium salts are
paler than the rubidium.
The hydrates of hydroxyazo-compounds also appear as representatives of two chromo-isomeric series.
The following are the colours of the hydroxyazo-compounds and of their
hydrates (0.5 or 1 mol. H,O) : o-Chlorobenzeneazophenol, red, yelIow ;
meta-compound, yellow, red ; para-compound, yellow, yellowish-red ;
o-bromobenzeneazophenol, red, yellow ;, meta-compound, yellow, red ;
para-compound, yellow, red ; o-tolueneazophenol, yellow, yellow ; metacompound, yellow, yellow ; benzeneazo-m-cresol, yellow, yellow ;
m-chlorobenzeneazo-m-cresol,
yellow, red ;o-tolueneazo-m-cresol, yellowish-red, yellowish-red ; benzeneazo-o-chlorophenol,
yellowish-red (labile),
yellow (stable), yellowish-red. The last-mentioned colour in each case
refers to that of the hydrate.
The determinations of the absorption spectra and of the molecular
extinctions of solutions of the salts and hydrates show that the yellow
and red forms are not polymorphous or polymeric. The solutions in
indifferent solvents have much the same colours as the solid salts.
The nature of the solvent also affects the colour of the solutions, the
more positive the nature of the solvent (namely, pyridine) the deeper
the colours. These solutions of salts of hydroxyazo-compounds are
regarded as equilibrium mixtures of yellow and red salts, just as in
the case of the violurates. From such solutions the ornnge-coloured
additive compounds (1 mol. yellow, 1mol. red, 1 mol. solvent) separate,
as they are sparingly soluble. All these solid additive compounds have
practically the same colour, so that the effect of different solvents on
the solids is practically nil ; since, however, the solutions have different
colours it is probable that the relative amounts of red and yellow salts
in the different solutions vary considerably. The increase in colour of
the salts, as compared with the free hydroxy-compounds, indicates that
salt formation as a rule favours the formation of the red form. It is
shown that mere salt formation (Gorke) has not necessarily a n auxochromic effect, since lithium salts are paler than the free hydroxycompounds, and dipropylamine salts in some cases give absorption
curves exactly analogous to those of the free hydroxy-compounds.
The following structural valency formulae are suggested for the
yellow and red forms :

i. 205

ORGANlC CHEMISTRY.

where the dotted lines represent subsidiary valencies.

The following values for the molecular extinctions (A=546) of
hydroxyazobenzene and its salts in different media at 15' and V = 2 0 0
are given :
Rubidium salt i n pyridine 510, in ethyl acetate Sl,-in:alcohol;44 ;
caesium salt in alcohol 24, in benzene + 4% alcohol 18, i n hexane + 4%
alcohol 14 ; lithium salt in ether 12 ; dipropylamine salt + 100 mols.
dipropylamine in benzene 9 ; hydroxyazobenzene i n carbon tetrachloride 8, in chloroform 7, in pyridine 7, in benzene 7, in alcohol 4.
The values for the molecular extinctions (A = 546) for salts of dibromohydroxyazober,zene a t 15' and P= 400 are :

Solvent
Ether ............
Alcohol ........
Pyridine.. .......

Li.

Na.

li.

Rb.

cs.

15
39
140

17

18
35
180

18
35
21 0

220

37
179

36

J. J . S.

Formation and Decomposition of Symmetrical Bisazocompounds of Ethyl Arylhydrazonemesoxalylbishydrazoneacetoacetates and of Ethyl Malonylbiahydraeoneacetoacetate. CARL BULOWand C. BOZENHARDT
(Ber., 1910, 43,
234--242).-Ethyl
malonylbishydrazonebenzeneazoacetoacetate reacts
with one molecule of benzenediazonium chloride, yielding ethyl phenylhydrazonemesoxalylbishydrazonebenzeneazoacetoacetatewith 72% yield
(compare Abstr., 1908, i, 253). I n addition, small quantities of ethyl
benzeneazoacetoacetate, cyclomalonylhydrazide, and 4-benzeneazo-3met hy 1-5-pyrazolone are formed. Et h y 1 p heny lhy drazonemesoxaly1bishydrazonebenzeneazoacetoacetate, when warmed with phenylhydrazine, decomposes i n t o 4-benze neazo-1-phenyl- 3-met hylpyrazolone
(orange needles, m. p. 154-155'
; yield 85%), 4-bemxenenxopy~axolidone
(m. p. 266"), and hydrazine. When boiled with dilute potassium
hydroxide, it yields 4-benzeneazo-3-methyl-5-pyrazolone
and mesoxalic
acid-phenylhydrazone ; whilst by the action of boiling acetic acid
4-benzenenzo-3-methyl-5-pyrazolone,
ethyl benzeneazoacetoacetate, and
4-benzeneazo-3 :6-pyrazolidone are produced. Dimethyl mesoxalatephenylhydrazone (compare Abstr., 1905, i, go), when treated with
m. p.
hydrazine hydrate, yields rnesoxalylphenylhydraxonedihy~rc~z~d~,
164O. The diacetyl derivative has m. p. 246-247'.
The dihydrazide
condenses with ethyl benzeneaxoacetoacetate, giving ethyl phenylhydrazooemesoxalyLbishydrazonebenzeneazoacetoacetate, the constitution of which is coDfirmed by this mode of preparation. The above
dihydrazide when boiled with acetic acid also yields 4-benzeneazo-3 :5pyrazolidone of m. p. 2 6 6 O , already mentioned. Ethyl phenylhydrazonemesoxalylbishydrazonebenzeneazoacetoacetate is also produced
by condensing equimolecular quantities of benzenediazonium chloride
and ethyl ~nalonylbishydraxonebenxeneaxoacetoacetate. The latter is

i. 206

ABSTRACTS OF CHEMICAL PAPERS.

formed in 80% yield by the condensation of 2 molecules of ethyl benzeneazoacetoacetate with malonyldihydrazide. It is decomposed by
boiling alcohol into ethyl malonate and 4-benzeneazo-3-methyl-5 pyrazolone. On heating, it melts at 128', then gas is evolved, and the
mass solidifies, melting again at 217-218'.
I n this process the
theoretical quantity of alcohol is evolved, and the residue consists of
4- benzeneazo-3-methyl-5-pyrazoloneand 1 : 1-maZonylbis-4 -6enzeneazo3methyZ-5-pyraxolone (compare Abstr., 1907, i, 986), m. p. 225.5O. On
boiling with potassium hydroxide or pyridine, the latter yields
4-benzeneazo-3-methyl-5-pyrazolone
and malonic acid.
Ethyl malonylbishydrazoneacetoacetate yields with 3 molecules of
p-diazotoluene chloride, ethyl-p-tolylhydrazonemesoxaZytlbishydrazoneto2uene-p-axoacetuacetate, orange needles, m. p. 209-2 10'.
By the
condensation of rnalonyldihydrazide with ethyl toluene-p-azoacetomatlo~ylbishydraxonetohenep-axoacetoacetate,
orange
acetate, ethyl
R. V. S.
needles, m. p. 114-115',
is produced.

Aeo-dyes derived from 2 :4Dimethylpyrrole and Hmmopyrrole. LEON ~ ~ A R C H L E W S K I and J. ROBEL (Ber., 1910, 43,
260-266 *).-For
the purpose of comparison with the azo-dyes
obtained from hsmopyrrole and chlorophyllpyrrole, the authors have
investigated the diazotisation of dimethylpyrrole. I n addition to the
monoazo-derivative of Plancher and Soncini (Abstr., 1901, i, 432), they
have obtained small quantities of a substance, C,,H,,N6Cl, which they
It
suppose to have the formula : (N,Ph*C6H7NoC,H~NoN,Yh)HC1.
crystallises in well-developed red needles having a metallic lustre, and
it is only slightly soluble in most solvents. I n physical characteristics
(including the absorption spectrum) the substance shows similarity to
R. V. S.
the azo-derivative of hamopyrrole.

Reduction of Nitroso-derivatives of Acetyl- and Benzoylhydrazobenzene. Lours NOMBLOT

(Compt. rend., 1910, 150,
338-339).-~~&rosoacety~hydrazobenxene,XAcPh-NPh-NO, obtained
by adding ethyl nitrite to acetylhydrazobenzene suspended in alcohol,
occurs in yellow prisms, m. p. 65". The corresponding 6enxoyZ derivative
crystallises in pale yellow leaflets, m. p. 116.5". The action of reducing
agents on these two substances has been studied. An alcoholic
solution of hydrazine hydrate converts them into the corresponding
acidylhydrazobenzene, with liberation of ammonia.
Aluminium
amalgam gives aniline, together with acetanilide or benzanilide. Zinc
dust in presence of acetic acid at 0-5" gives no reduction products.
Under no conditions were triazan derivatives obtained.
W. 0. W.

[Preparation of p - Aminophenyl-2-azimino-5naphthol-7sulphonic Acid.] GESELLSCHAFT

FUR UHEMISCHE
INDUSTRIE
IN BASEL
(D.R.-P.
2 14658).-p- Aminophenyl-2-azimino-5-naphthoL7-sulphonic
acid, a grey, crystalline powder sparingly soluble in water and
employed in the production of Bordeaux-red dyes, is prepared by the
following series of operations :
l-Chloro-2 : 4-dinitrobenzene is condensed with p-naphthylamine* and Bull. Acad. Sci. Cracow, 1910, A , 1-8.

i. 207

ORGANIC CHEMISTRY.

5 :7-disulphonic acid, yielding 2 : 4-dinitrophenyl-P-naphthylamine5 :7-disulphonic acid ; this is reduced with sodium sulphide and
ammonium chloride to p-nitro-o-aminophenyEP-naphthylamim-5
: 7disulphnic acid, the disodium salt of which forms red, crystalline
leaflets. This substance is treated with sodium nitrite i n the presence
of sulphuric acid, and the resulting nitroaximino-compound reduced
with iron rilings to p-aminophenyl-2-axirninonaphthalene-5
: 7-disulphonic acid, grey needles, which, on heating with sodium hydroxide
solution a t 180- 190, yields the foregoing naphtholsulphonic acid.
F.M. G. M.

Azoarylhydrazinesulphonic Acids. JULIUS TROGERand A.

WESTERKAMP
(Arch. Pharm., 1909, 247, 657--698).-The
hydrazinesulphonic acid, obtained by the action of sulphur dioxide on aqueous
benzenediazonium sulphate (Abstr., 1904, i, 118 ; 1906, i, 120, 9 9 3 ,
994), has been synthesised b y Troeger and Puttkammer (Abstr.,
1907, i, 263) by converting diazotised aminoazobenzene into azobenzenediazosulphonate, and reducing the latter by ammonium
sulphide :
NzE'h*C,H4*NHz-+ N2Ph*C6H4*N2C1
-+ N2Ph*C6H,*N,*O*S02K
(Labile salt.)

-+ N2Ph*C6H4*N2*S03K
-+ N2Ph*C6H4*NHoNH*S03H.
(Stable salt.)

This synthetic process has now been applied t o numerous aminoazocompounds, whereby hydrazinesulphonic acids are obtained, which are
red, blue, violet, or brown; they are best purified by means of their
salts with aromatic amines, and are reduced by stannous chloride and
hydrochloric acid in the sense of the equation :
N2Ph*C,H4.NH*NH*S03H
+ 6 H + H,O =
NH2Ph -tNH2*C6H,*NH,
+ NH, + H,S04,.
a monoamine and a diamine always being formed. When heated
with alcoholic hydrogen chloride and a n aldehyde or ketone, the
hydrazinesulphonic acids lose the sulphonic acid group, and are converted into hydrazones which form coloured salts with the hydrochloric
acid.
4-Amino-o'm-azotoluene thus yields a reddish-brown o'm-azotoluerne4-hydraxinesulphonic acid, C,H4Me*N2*C,H3Me-NH*NH*SO,H (the
potassium and ba~iumsalts are described ; the p-toluidine salt,
Cl,Hl,N4*S03~NH,'C,H7,
m. p. 158q forms yellow needles), which yields o-toluidine and
1 : 2 :5-tolylenediamine by reductive fission, and in the presence of
alcoholic hydrogen chloride reacts with salicylaldehyde t o form
o-hydroxybenxylidene-o'm-axotoluene-khydraxone,
C,H4Me*N2*C,H,Me*NH*N
:CH*C6H4*
OH,
m. p. 130-131O (the hydrochloride, C21H210N,C1,forms violet needles,
and the sulphute, blue ueedles with :t green reflex), with p-nitrobenzaldehyde to form a similar hydrazone,
C,H,Me*N,*C,H,Me*NH*N :CH*C,H,*NO,,
m. p. 158O, with p-methoxybenzaldehyde to form the reddish-yellow

i. 208

ABSTRACTS OF CHEMICAL PAPERS.

hydraxone, C22H220N4,
m. p. 147', and with benzaldehyde to form an
orange-red hydrazone, C,,H,,N,, m. p. 160'.
4-Amino-mp'-azotoluene yields reddish-brown, amorphous mp'-azotoluene-4-hydrazinesuZphonicacid$ C1,Hl6O3N,S,the p-toluidine salt of
which, m. p. 183O, forms yellow needles; the hydrazone, C2,Ha20N4,
m. p. 14
8', from p-methoxybenzaldehyde forms golden-yellow leaflets ;
the hydrazone, C,1H200N,,m. p. 120-121',
from salicylaldehyde forms
red prisms, and the hydrazone, C21H,902N5,
m. p. 176-177',
from
m-nitrobenzaldehyde is a reddish-brown, crystalline powder.
op'- Axotoluene-4-hydraxinesuZphonic acid, C14H,,o3N,S, obtained
from 4-amino-op'-azotoluene, is a dark reddish-brown, amorphous
powder ; the p-tohidine salt, m. p. 171', forms reddish-yellow
needles. mp'-AzotoZuene-6-hydraxinesuZphonic acid, C,,H1,0,N4S, is
a n indigo-blue, amorphous powder obtained from 6-amino-op'-azotoluene ; the p-toluidine salt has m. p. 154', and the aniline salt has
m. p. 1 39'.
Benxeneazo-p-toluene-4-hydrazinesuZphonic
acid,
C,,H,*O,N,S9
is a dark red, amorphous powder, which forms a yellow, crystalline
p-toluidine salt, m. p. 170' (decomp.), arid a p-xylidine salt, m. p.
175' (decomp.). Benxeneaxo-p-xylidine, N,Ph*C,H,Mo,'NH,,
m. p.
104-105, obtained by the slow addition of diazotised aniline hydrochloride to a n alcoholic solution of p-xylidine and treatment of the
resulting hydrochloride with ammonium hydroxide, separates from
dilute alcohol in golden leaflets, and from petroleum and benzene as a
deep orange, crystalline powder, and forms a nitrate crystallising in long,
blue needles, a violet hydrogen sulphate, and a golden-yellow oxalate.
It is converted by the usual processes into 6enxeneaxo-2 :5-xyZene-4?..ydra&esuZ'honic
acid, C,H,O,N,S,
a dark red, mioro-crystalline
powder, the reddish-yellow p-toluzdzne salt of which has m. p. 158'.
Benxeneaxo-a-naphth y lhydrazinesuZphonic acid,

N,Ph*C,,H,*NH*NH SO,H,
obtained from benzeneazo-a-naphthylamine,is a n amorphous, violet
powder, which is best purified by means of its potassium salt,
C16H1303N4SK,

which crystnllises in reddish-yellow needles. The acid is reduced by

zinc dust and hot acetic acid, y!elding aniline and 1 :4-naphthylenediamine, and reacts with alcoholic hydrogen chloride and aldehydes i n
the manner mentioned, hydrazones being produced in the form of
hydrochlorides ; the hydrazone, N,Ph*C,oH6*NH*N:CH*C,H4*OMe,
m. p. 258-160',
from p-methoxybenzaldehyde forms orange needles
(hydrochloride, deep blue needles) ; the hydrazone from salicylaldehyde
has m. p. 205' (hydrochloride, bluish-violet needles) ; the hydrcmonefrom p-nitrobenzaldehyde has m. p. 172-1 73" (hydrochlokle, dark
green powder).
I n a similar manner, benzeneazo-P-naphthylamine yields benzene
axo-P-nuphtAyZhydraxinesuZphonic acid, a coffee-coloured, amorphous
powder, which is purified through the p-toluidine salt, m. p. 1 6 5 O
(decomp.).
2 :4 : 3' : 5'-Tetrurnethylaxobenzene-2-hydrazinesulphonicacid,
C6H,Me,~N,*C,~,Me2~~H*~~*S~,H,

i. 209

ORGANIC CHEMISTRY.

obtained from aminoazo-m-xylene, is a red, amorphous powder, which

forms a p-tohidine salt, m. p. 170 (decomp.), aniline salt, m. p.
153 (decomp.), and a p-xylidime salt, m. p. 176O (decomp.).
a-Napht hylazo-a-naphthy2hydrazinesulphonic acid,
C,,H7*N,C,,H,*N H *NH SO,H,
obtained from aminoazo-a-naphthalene, is a dark blue substance.

c. s.

The Adsorption of P r o t e i n s , WILHELM

BILTZand XANSSTEINER
(Biochem. Zeitsch., 1909, 23, 27-42) -The adsorption of egg-white by
cellulose, iron hydroxide, and kaolin mas estimated in varying concentrations of the protein. The amount adsorbed was determined by
estimating the nitrogen in the clear solution, after filtration of the
adsorbent, by a modification of Kjeldahls method, the amount of
ammonia being determined colorimetrically with the use of Nesslers
reagent. The adsorption process is not entirely reversible, and the
results do not entirely agree with the ordinary adsorption equation.
The application of the adsorption formula to the combination of toxin
and antitoxin was also investigated (1 - T/VA
= log L + l/p log T,where T
is theconcentration of the free toxin, and 1- 27 t h a t of the combined).
The results of the neutralisation of tetanolysin and streptolysin by
the antilysins, and of the streptolysin by cholesterol, of diphtherotoxin
by its antitoxin, of saponin by ox-blood, of cobralysin by antivenin,
and other similar reactions were investigated. The results obtained
were compared with those calculated from the adsorption equation and
Arrhenius mass reaction equation. Neither of these equations agreed
in a satisfactory manner with the results obtained experimentally.
S. B. S.
Composition of the Products of the Alkaline Hydrolysis of
Cryatalline Egg-albumin. NOGENDRAMOHON
GUPTA(Monatsh., 1909,
30, 767--771).--The
products resulting from the hydrolysis of eggalbumin by sodium hydroxide (compare Skraup and Hummel burger,
Abstr., 1909, i, 340) have been submitted to careful analysis, with the
following results :
Protalbic acid .... ...
Lysalbic ,, .........
Lysalbinpeptone ......

Carbon.

55.4
52 -9
46-2

Hydrogen.
7.2
7.0
6.6

Nitiogeii.
14.3
14 -9
103

Sulphur.
24
1-2
1.2

W. H. G.
The Preparation and P r o p e r t i e s of Iodo-Mucoids. GUSTAVE
M. MEYER(J. Biol. Chem., 1909, 7, 11-lG).-Iodo-mucoids
were
prepared by the action of iodine on tendo-mucoid in a dilute solution of
sodium carbonate ; they contain approximately 14% of iodine.

W. D. H.
The Relation of Proteins t o Crystalloids. I. The Osmotic
Pressure of Hmmoglobin and the L a k i n g of Red Bloodcorpuscles. HERBERT
E. ROAF(Quart. J. exp. Physiol., 1910, 3,
75--96).-A
simple method is described for the direct measurement
of the osmotic pressure of a solution when the solute does not pass

i. 210

ABSTRACT@ OF CHEMICAL PAPERS.

through parchment paper or other suitable membranes. Ia this way

the osmotic pressure of laked corpuscles and crystallised haemoglobin
was measured, and pressures corresponding with the molecular weight
of haemoglobin calculated from other data were obtained if conditions
obtain which limit ionisation ; but otherwise much higher pressures
are reached, and it is suggested that this is due t o the ionising of
hsmoglobin salts; both acid and alkali increase the pressure, and as
with serum proteins, a minimal pressure is found near the neutral
point. Many substances lower the osmotic pressure, and thus might
help to prevent laking of red corpuscles. Pressures were obtained
with corpuscles laked by freezing and thawing up to 282 and 256, If
ionisation occurred, the calculated pressure might be as high as 960 mm.
of mercury. With such a range of pressure, the osmotic pressure of
haemoglobin should be considered in discussing the laking of corpuscles,
but until further experiment has determined the pressures in mixed
solutions containing the various crystalloids of the corpuscle, it cannot
be decided what part is played by haemoglobin and how much is due t o
other factors.
W. D. H.

Blood Colouring Matter. WILLIAMKUSTER(Ber., 1910, 43,

370-375).-The
compound, C36H3603N4,
obtained by Kuster and
Fuchs (Abstr., 1907, i, 572) as a bye-product of the action of aniline
on haemin is also formed in small quantity when acetglhaemin is converted into dehydrochloridehaemin. By the action of concentrated
hydrochloric acid under pressure on haematin, the organic material
partly loses its acid properties and partly undergoes oxidation. Haemin
and haematin are regarded as ferric compounds, and the ferric chloride
formed oxidises part of the iron-free haematin. The oxidation product
does not undergo rearrangement to haematoporphyrin. When hydrogen
bromide is used, the oxidising action of the ferric bromide is neutralised,
and haematoporphyrin formation takes place. Ten % hydrochloric
acid only eliminates 5% of. the iron from hsmin a t 130, whereas
under similar conditions over 90% of the iron is separated from
hzematin.
Haematin is slowly changed by solution in alkali, whereas the fresh
solution is completely precipitated by the theoretical quantity of barium
chloride. After keeping, a large excess of this is required. Polymerisation to a p-haematin takes place on keeping.
The conversion of haematin by reducing agents into haemochromogen
is regarded as corresponding with a reduction from the ferric to the
ferrous state. Haemoglobin contains ferrous iron ; oxyhsemoglobin,
however, contains iron peroxide.
Haemin forms salts with 3 mols. of alkali hydroxide; dehydrochloridehaemin, salts with 2 mols. These can be dialysed in 1% solution
without the dye passing through. H s m i n only takes up 2 mols. of
sodium carbonate, and sodi um hydrogen carbonate appears in the outer
water on dialysis. Precipitates obtained with other metallic salts
showed zt very varying metal content.
The iron salts dissolve in sodium hydroxide and are acids ; seemingly,
the second iron atom is attached to the free nitrogen atom.
E. F. A.

ORGANIC CHEMISTRY.

i. 211

Bshaviour of Gelatinous Substances or Collains towards

C a r b o n Disulphide. WL. S. SADIKOFF
(J.Russ. Phys. Chern.XOC.,1909,
41, 1597-1686 ; Kolloid. Chem. Beihefte, 1910, 1, 119--220).-When
anialkali acts on glutin i n presence of carbon disulphide, thiohydration occurs, this consisting of two distinct processes, namely,
hydration by the alkali and subsequent addition of carbon disulphide
or thionylation (compare A bstr., 1907, i, 740). The most characteristic part of the thionplglutin thus obtained is the complex to
which the carbon disulphide is added, and which is termed the
receptor.
This receptor is extremely indifferent, neither being
destroyed by water, reacting with tannin, bromine, aldehydes, or
the majority of organic acids, nor being replaced by benzoyl chloride
or methyl iodide. I t takes up carbon. disulphide in neutral, alkaline,
or acid media, combines with strong mineral acids, and with acetic
and oxalic acids, is substituted by trinitrophenol and immobilised,
or rendered incapable of taking up carbon disulphide, by solutions
of sulphates, probably owing to the sulphuric acid formed by
adsorptive decomposition of the salts.
I n the case of tendo-collagen, the receptor is not homogeneous.
The predominating part of it is readily reactive, being replaced by
carbonic acid, and by organic and mineral acids, acetic anhydride,
benzoyl chloride, bromine, methyl iodide, or aldehydes ; it is stable
towards the action of heat or water, and is not replaced by picric
acid. The lesser part of the receptor is highly inert, is replaceable
only by mineral acids and tannin, and is stable towards the action of
water, but thermo-labile; this part is not altered by the action of
alkali hydroxide. The reactive portion of this receptor would seem
to be a primary or secondary amine.
T.H. P.

The Scission Products R e s u l t i n g from the Partial Hydrolysis

of Proteins. EMILABDERHALDEN
(Zeitsch. physiol. Chem., 1909, 63,
40 1-404).-From
the partial hydrolysis of silk, .glycyl-2-tyrosine was
obtained previously.
The present research gives details of the
preparation and identification of another dipeptide from the same
source, namely, d-alanyl-glycine.
W. D. H.
Trypsin and Antitrypsin. KURT MEYER(Biochem. Zeitsch.,
1909, 23, 68--92).--Samples
of dried pancreatic juice and juice from
the small intestine were used in the experiment, and dissolved t o give
the necessary concentrations as required. The tryptic action was
estimated by the Gross-Fuld casebogen method. The influence of the
quantity of kinase on the activation of the trypsinogen was first
investigated. The results indicate that the kinase action is of fermentlike character. The grade of activation is not proportional to the
amount of kinase, and very small quantities of the latter can activate
large quantities of the trypsinogen, provided t h a t sufficient time is
allowed for the action. The rate of activation is approximately
proportional to the amount of kinase. The greater activity of
mixtures containing large amounts of kinase is apparently due to a
shortening of the activating process, owing to which the concurrent
destruction of the trypsin and kinase becomes less marked. A n
excess of kinase does not inhibit the activation. The inhibitory

i. 212

ABS'I'RACTS OF CHEMICAL PAPERS.

substance of the serum is neither an antikiriase nor a n antitrypsinogen. The former possibility is excluded by the fact that the
anti-action is not overcome by the addition of excess of kinase, and
is also exerted on trypain which has been obtained from trypsinogen
by calcium salts. Antitrypsinogen and antikinase are also excluded
by the fact that the inhibitory action of the serum is not increased
by allowing it to act on the kinase or trypsinogen alone before
mixture, and that the quantity necessary for inhibiting a mixture
which is being gradually activated depends on the amount of trypsin
actually present at the time of addition.
No an titrypsinogen or antikinase could be obtained by immunisation
experiments.
The saturation of trypsin by the anti-substance
follows the lam of multiple proportions.
I n the fractional saturation
of trypsin by the anti-substance, the Danysz phenomenon was
observed, namely, the inhibitory action is weaker than if the whole
quantity of anti-substance had been added at one time.
Previous treatment of trypsin by antitrypsin did not increase the
inhibitory effect. The formation of a non-digesting, but antisubstance binding trypinoid could not be effected, The effect of
heating trypsin and the anti-substance was also investigated. The
results indicate that antitrypsin is not a negative catalyst, but
actually enters into combination with trypsin. No kind of specificity
S. B. S.'
was noted in the case of antitrypsin.

Influence of the Reaction of the Medium on the Filtration

of Diastases. MAURICEHOLDERER
(Compt. rend., 1909, 149,
1153-1 156).-Details of experiments on extracts of A8pergillus nigei.
are given, from which it appears that a porcelain fiker is permeable to
sucrase when the solution in which this is present is neutral to
phenolphthalein ; when the solution is neutral to methyl-orange,
however, the ferment no longer passes the filter. I n order, therefore,
to render the extraction of sucrase more complete, it is desirable
to have the solution alkaline whilst maceration is i n process.

w. 0.w.

Influence of the Reaction of the Medium on the Filtration

of Malt Enzymes. MAURICE
HOLDERER
(Compt. rend., 1910, 150,
285-288.
Compare preceding abstract).-The
enzymes of malt,
amylase, dextrinase, and peroxydiastase resemble the diastases already
studied in their behaviour when the solutions are filtered through
porcelain. Filtration occurs readilyFwhen the solutions are neutral
to phenolphthalein, but the passage of the enzymes through the filter
W. 0. W.
is inhibited if the medium is neutral to methyl-orange.

Cellase and the Diastatic Decomposition of Cellose.

GABRIELBERTRAND
and MAURICE
HOLDERER
(Compt. rend., 1909, 149,
1385--1387).--9n
attempt to ascertain whether a specific ferment
exists capable of hydrolysing cellose.
Maltase and sucrase are
without action on this substance, whilst a maceration of Aspergillus
niger converts it completely into dextrose. Preparations of emulsin
from almonds, and of emulsin with trehalase from barley o r malt,
have the same action.
w. 0. w.