[CONTRIBUTION FROM THE CHEMICAL LABORATORIES OF THE UNIVERSITY OF

NOTRE DAME]
THE ADDITION OF ACETYL CHLORIDE TO
ALKYLACETYLENES*
JOHN W. KROEGER, FRANK J. SOWA, AND JULIUS A. NIEUWLANDt
Received February 14, 1996
INTRODUCTION
A number of reports concerning the reactions of acyl halides with
01efins~~~J have been presented in the literature, but none on the analogous
addition to acetylenic hydrocarbons. Acetyl chloride has been reported
to add to olefins to form saturated chloro ketones which lose hydrogen
chloride on distillation. The chloro ketones from acetylenic compounds
were found to distill undecomposed and lost hydrogen chloride only to a
slight (extent even after standing for rather long periods of time.
Krapivin,* in his report on the condensation of olefins with acid chlorides
in the presence of aluminum chloride, mentioned as by-products halogen-
substituted, saturated hydrocarbons of the series C,H2,+1X, which ob-
viously are formed by the addition of hydrogen chloride to the double
bond in a manner analogous to the formation of the chloro olefins herein
described.
Daraens3 carried out a very careful investigation along similar lines and
found that, of all the catalysts tried, anhydrous stannic chloride gave the
best results. His conclusions were verified in the present investigation,
and stannic chloride was selected from a number of covalent metal chlorides
which were found to catalyze the reaction. These included zinc chloride,
aluminum chloride, antimony pentachloride, phosphorus tri- and penta-
* Paper VI11 on the addition reactions of alkyl acetylenes. Previous paper,
.T. Am. Chem. Soc., 68, 80 (1936).
t Dr. Nieuwland, a member of the Board of Editors of THIS JOURNAL, died
suddenly of a heart attack on June 11th [ Znd. Eng. Chem., News Ed., 14, 248
(June 20, 1936)l.
1 KCINDAKOW, Bull. SOC. chim., 7,576 (1892); ZELINSKI, J . Russ. Phys. Chem. SOC.,
31, 402 (1899); BLANC, Bull. SOC. chim., 19, 699 (1890); NORRIS AND COUCH, J . Am.
Chem. SOC., 42,2329 (1930); WIELAND AND BETTAQ, Ber., 66, 2246 (1922); SCHOELLER
AND ZOLLNER, U. S. Patent 1,737,203 (Nov. 1929).
* KILAPIVIN, Bull. Soc. Imp. Nut. MOSCOW, 1, (1908); Chem. Abstr.; 6, 1281 (1911).
a DARZENS, Compt. rend., 160, 707 (1910).
163
164 J. W. KROEGER, F. J. SOWA, AND J. A. NIEUWLAND
chlorides, phosphorus oxychloride, mercuric chloride, and cuprous chloride.
Stannic chloride in amounts greater than 401, caused an immediate violent
reaction. I n addition it had the advantage of being completely soluble
in the reaction mixture.
We found that acetyl chloride reacts with alkylacetylenes in the pres-
ence of catalysts to form, mainly, chloro-olefinic ketones together with
smaller amounts of 2-chloro-1-olefins and traces of alkyl acetates. The
principle reaction is :
R-CeC-R' + CH-CO-Cl-+ R-C=C-CO-CH,
I 1 (A)
C1 R'
(R' =hydrogen or R)
The chloro-olefinic ketones are pleasant-smelling liquids, and have a
light yellow color when freshly distilled, but darken slightly on standing.
They decompose readily in the presence of traces of acid but can be kept
indefinitely by the addition of a small amount of anhydrous potassium
carbonate. They have a slight vesicant and lachrymatory action which
decreases with increase in the molecular weight of the compound. They
were found to be oxidized to some extent by air-especially the lower
members of the series. I n the case of the lowest member of the group,
4-chloro-3-hexene-2-one, a temperature of 75" was reached by bubbling
air through the pure substance.
The cis and trans isomers of these ketones were found to be rather
readily separable and were isolated in certain cases. On standing for a
few weeks the pure isomers reverted completely to an equilibrium mixture.
By analogy to the known pairs of liquid cis-trans isomers, the higher-
boiling fraction has been designated cis and the lower-boiling, trans. This
assignment is supported by the fact that an alcoholic solution of sodium
acetate gives an almost immediate precipitation of sodium chloride with
the trans isomers of the normal ketones, while several days are required
for the precipitate to form from the cis isomers; moreover when hydrogen
chloride is added to an acetylenic ketone the product is mainly the trans
isomer. Hydrogen chloride is generally conceded to add to and split out
from the trans positions.
By keeping the amount of catalyst low, usually 2 to 4% of the mixture,
the reaction was prevented from going to completion. I n spite of this
precaution the reaction was always accompanied by the formation of
some tarry polymerized products. The yields were usually from 20 to
35% of the chloro olefin and from 25 to 40% of the ketone. The larger
yields of chloro olefin were obtained in the case of the dialkylacetylenes.
Traces of alkyl acetates were also formed, and could not be accounted for.
ADDITION OF ACETYL CHLORIDE TO ALKYLACETYLENES
165
Both hexyne-1 and decyne-5 formed about 1% of n-butyl acetate, which
was identified by fractionation and saponification.
A satisfactory explanation for the formation of the chloro olefin, as yet,
has not been advanced. The following mechanism might be considered
plausible :
CHrCO-Cl*+ CH?C=O + HC1 (B)
Hydrogen chloride and ketene might then react with the alkylacetylene as
follows:
R-CrCH + HC1----+ R-CCbCHZ (C)
(D)
HC1
R-C=CH + CH?C=O -+R-CZZC-CO-CH~
R-CCl=CH-CO-CH3
And in the case of dialkylacetylenes:
R-C-C-R + HC1- R-CClECH-R (E)
R-C=C-R HC1
[ H2&--&=0] - (F)
R-CeC-R + CH?C=O -+
R-CCkCR-CO-CH,
Direct addition of acetyl chloride to the triple bond might also take place
as written previously (A).
The acetylenic ketones were found to add hydrogen chloride very readily,
which may explain the fact that no such ketones, nor those of the cyclo-
butenone type, were isolated.
EXPERIMENTAL
Mai'eria1s.-The monoalkylacetylenes were prepared from the corresponding
alkyl bromides and sodium acetylide in liquid ammonia. The sym-dialkylace-
tylenew were prepared in a similar manner from the sodium compound of the mono-
alkylacetylenes. Commercial acetyl chloride was fractionated and the fraction
boiling from 50.0 to 50.5" was saved. Stannic chloride, anhydrous, was used after
redistillation.
The, procedures for the preparation of the ketones were all quite similar and a
description of one such preparation will be sufficient.
Addi t i on of acetyl chloride to hezyne-1 .-In a three-liter, three-necked flask,
equipped with a reflux condenser, dropping funnel and mercury-sealed stirrer, was
placed 850 g. (10.4 moles) of hexyne-1, b.p. 70.0 to 70.5", and 820 g. (10.4 moles) of
acetyl chloride. To this mixture, which was stirred vigorously, a solution of 40 g.
of anhydrous stannic chloride i n 100 g. of acetyl chloride was added dropwise. The
addition was carried on rapidly enough to keep the reaction mixture refluxing slowly.
The color of the solution changed rapidly from yellow to dark-red. The mixture
was then refluxed for one hour.
166
I
I1
I11
I V
V
VI
VI 1
VI11
IX
X
XI
XI 1
XI11
XI V
J. W. KROEGER, F. 3. SOWA, AND J. A. NIEUWLAND
TABLE
PHYSICAL CONSTANTS AND ANALYSES OF ADDITION COMPOUNDS
COMPOUND
~~
4-chloro-3-ethyl-
3-hexene-%one
(trans)
4-chloro-3-ethyl-
3-hexene-2-one
(cis)
4-chloro-3-n-
propyl-3-
heptene-2-one
(t rans)
4-c hloro-3-n-
propyl-3-
heptene-2-one
(cis)
butyl-3-octene
-2-one
amyl-3-nonene
-Zone
4-c hloro-3-
hexene-2-one
4-chloro-3-
heptene-2-one
(trans)
4-chloro-3-
heptene-2-one
(cis)
4-c hloro-3-
oc tene-2-one
(trans)
4-chloro-3-
oc tene-2-one
4-chloro-3-n-
4-chloro-3-n-
(cis)
4-chloro-3-
nonene-Zone
(trans)
-chloro-3-
nonene-2-one
(cis)
3-c hloro-3-hexen<
b.p.
89-91/30 mm.
97-99'/30 mm.
112-113'/2$ mm.
117-118'/28 mm.
14O-I46'/28 mm.
115-121'/5 mm.
46-53'/10 mm.
54.5-55.5'/10 mm.
62-63'/10 mm.
69'/10 mm.
80/10 mm.
89"/10 mm.
99'/10 mm.
113.0-1 13.5'/
748 mm.
I
1 MOL. WT. 1 CHLORINB (%)
ADDITION OF ACETYL CHLORIDE TO ALKYLACETYLENES 167
COMPOUND
--
MOL. WT. I CHLORINE (%)
b.p. n: : df y
-
8
---
XV
XVI
XVII
XVIXI
XIX
xx
4-chloro-4-
octene
5-chlorod-decene
6-chloro-6-
dodecene
2-chloro-1-butene
2-chloro-1-hexene
2-chloro-l-
heptene
157.5-159.5'/
750 mm.
99-100/28 mm.
128-129'/28 mm.
57-59'/748 mm."
109.5-110.5'/
735 mm.
138-139'/748 mm.b
71-72'/75 mm.
1.4394
1.4448
1.4493
1.4115
1.4187
(21O)
(W
---
.43 24.2 23.4
75 20.3 19.4
96 17.5 17.C
-- -
- - -
-- -
0.8788 146 . E
0.8753 174.7
0.8760 202 .7
0.8950 -
0.8872 -
(21')
1.43020.8788 -
(24')
a Constants reperteds: b.p. 61-62', nD 1.4168.
Constants reported6: b.p. 71'/75 mm., d y 0.8895, n: 1.4349.
I n the case of the dialkylacetylenes, the mixture was hydrolyzed at this point.
Considerable time could be saved, when large quantities of ketone were desired, by
using the following procedure. This was particularly applicable where the ace-
tylene was low-boiling.
The unchanged acetyl chloride and hexyne-1 were distilled off with continued
stirring until the temperature reached 80". The residue was then washed with
water, 10% sodium carbonate, then again with water, and finally was steam-distilled.
The mixture of acetyl chloride and hexyne-I, amounting to 1040 g. was replaced
in this three-necked flask and 25 g. of stannic chloride was added. After refluxing
for one hour the unchanged reactants were again distilled off and the residue was
washed and steam-distilled as before.
This procedure was repeated twice more and the product of the fourth reaction
was hydrolyzed immediately after refluxing, then washed and steam-distilled. The
products after steam distillation were combined, dried over calcium chloride and
fractionated. Two hundred sixty gram8 (3.2 moles) of hexyne-1 was recovered.
Yields: 2-chloro-I-hexene (b.p. 107-111 "), 130 g. (1.1 moles), 15%; 4-chloro-3-octene-
2-one (b.p. 75-95"/20 mm.), 430 g. (2.7 moles), 37%.
The crude ketone was further fractionated* i n an all-glass apparatus with a
Widmer column with a packed section 35cm. long.
* This fractionation could be carried out only with quantities less than 200 g.
Attempts to fractionate larger quantities resulted in complete conversion to a
polymer, b.p. 174"/10 mm., n: 1.4705. Treatment of the simple ketone with 0.2%
of concentrated hydrochloric acid caused a quantitative conversion to this polymer
on sttinding for 24 hours. If distilled immediately the boiling point of the polymer
could be duplicated. On standing for three days over potassium carbonate i n dif-
fused sunlight the polymer reverted completely to the monomer. This compound is
obviously not a condensation product and it is possible that the formula may be
analogous to those of the truxillic acids.
THI JOURNAL OF ORQANIC CHEMISTRY, YOL. 1, NO. 2
168 J. W. HROEGER, F. J. SOWA, AND J. A. NIEUWLAND
(I ) Trans isomer: b.p. 69'/10 mm., n f 1.4657, d2: 0.9705.
(11) Cis isomer: b.p. 8Oo/l0 mm., n: 1.4721, dZ: 0.9984.
(I ) gave a semicarbazone which, after recrystallization from aqueous alcohol,
melted at 109-110". The semicarbazone of (11) melted at 121.0-121.5".
I n the reaction with butyne-1, b.p. 8", liquid ammonia, rather than water, was
circulated through the reflux condenser.
The Widmer column was used to fractionate the compounds from hexyne-1 and
heptyne-1 only. The other pairs of cis-trans isomers were fractionated through a
Vigreux type column 20 cm. long and of 10 mm. outside diameter, and consequently
were not quite as pure.
The semicarbazones of 4-chloro-3-nonene-2-one, the compound from heptyne-1 ,
were also prepared. Trans isomer, m.p. 127"; cis isomer, m.p. 137-138". An indi-
cation of the rapidity with which the cis-trans equilibrium mixture is formed from
the individual isomers was obtained from the fact that the semicarbazones of 4-
chloro-3-ethyl-3-hexene-2-one, the compound from hexyne-3, which were prepared
after the pure isomers had been standing for two weeks, both melted at 161".
Proof o j Structure.-3-Hexyne-P-one (b.p. 76"/15 mm., ii 1.4460, d: 0.8622) and
3-heptyne-Bone (b.p. 89-91"/15 mm., ng 1.4461, d*: 0.8780; reported, b.p. 91-95"/
18 mm., nf : 1.4453, do 0.8893) were prepared by a modification of the procedure of
Moureu and Delange4 using the following reaction:
R- CSC- MgCl + O(C0- CHs)2 ---t R-C=C- GO- CHa + MgCl(0-CO - CHI) (G)
Hydrogen chloride was added to these compounds in the following manner. The
acetylenic ketones were dissolved in chloroform, and the solution was cooled i n a
bath of liquid ammonia. Dry hydrogen chloride was passed into the cold solution
i n the presence of a trace of cuprous chloride. The absorption were quite rapid,
and after an hour the chloroform solution was removed, was washed first with water,
then with sodium carbonate solution, and was dried over calcium chloride. The
chloroform was distilled off, and the residue was again washed with sodium carbonate
solution, since at this point large amounts of hydrogen chloride were evolved. The
material was then dissolved i n benzene and dried over calcium chloride. The
liquid remaining after the benzene was removed, distilled, in the case of hexynyl
methyl ketone, at 67-70/10 mm.; n t 1.4625; dzJ 0.9720. The addition compound of
heptynyl methyl ketone had the following properties: b.p. 89-95"/10 mm. ; n:
1.4640; d:S 0.9824. The yields were quantitative. It may be noted that these physi-
cal constants compare favorably with those of the trans isomers given previously.
(See Table.)
The analyses for chlorine were conducted according to the method of Vaughn
and Nieuwland.' The molecular weights of all compounds except 4-chloro-3-octene-
2-one and 4-chloro-3-nonene-2-one were determined cryoscopically i n benzene. The
molecular weights of the latter compounds were determined in camphor by the
method of Rast.8
I n the reaction of acetyl chloride with pentyne-1, no chloro olefin was obtained.
Other acid chlorides, such as alkyl and aryl chlorocarbonates and aryl sulfone-
MOUREU AND DELANGE, i bi d. , 131, 710 (1900).
5 DUPONT, ibid., 148, 1522 (1909).
* BACHMANN AND HILL, J. Am. Chern. Soc., 66,2730 (1934).
7 VAUGHN AND NIEUWLAND, Ind. Eng. Chem., Anal. Ed., 3, 247 (1931).
* RAST, Ber., 66, 1051, 3727 (1922).
ADDITION OF ACETYL CHLORIDE TO ALKYLACETYLENES 169
chlorides were found to react with acetylenes and will be discussed i n a future
contribution.
Acknowledgement is made to Mr. G . M. Wolf for the preparation of the acety-
lenic ketones.
SUMMARY
1. The addition of acetyl chloride to alkylacetylenes has been effected
2, Several members of a new series of ketones and some new chloro
3 , A mechanism has been proposed for the formation of the chloro
with the aid of catalysts.
olefins have been prepared.
ol eh