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SEPTEMBER, 1948

481

PREPARATION OF ACYL CHLORIDES WITH THIONYL CHLORIDE


SAVER10 ZUFFANTI
Northeastern University, Boston, Massachusetts

SURVEY of organic chemistry laboratory manuals


shows that thionyl chloride, a common and widely
used reagent, is not even mentioned as a halogenating
agent in most of them. One manual (4) discusses the
purification of thionyl chloride and its use in preparing
henzoyl chloride from benzoic acid. A second book
(5) merely states "In recent years thionyl chloride
has also been brought into use. . . ; it has the advantage
that its decomposition products are gaseous and hence
do not interfere with the working up of the reaction
mixture." Most of the other manuals make no
mention whatsoever of thionyl chloride.
Numerous laboratory experiments involving. the
use of phosphorus halides can be found in the literature, but only two papers (1, 7) were found which deal
with the use of thionyl chloride. A comparison of the
following equations, however, points out the advantage
'of thionyl chloride as a halogenation agent.
R-COOH + PCl, -. R-COCl
HCl (g)
POClr

R-COOH

+ SOCl*

-r

R-COCl

+
+ HCl (a) ++ SO* (a)

The following directions for this experiment have


been very carefully checked and with a reasonable
amount of care the students will find them highly satisfactory.
Ezperimental. In a 250-ml. distilling flask fitted
with a separatory funnel is placed 20 grams (0.147
mole) of o-toluic acid. The side-arm of this flask is
attached to a long downward condenser, which in turn
is connected by means of an adapter to a 500-ml.
filter flask. A calcium chloride drying tube is joined
by a short piece of rubber tubing to the tubnlature of
the filter Bask. While the flask containing the acid is

heated on a water bath which is kept at 60-65', a 20ml. (32.75 grams, 0.275 mole) portion of freshly distilled thionyl chloride is gradually added from the
separatory funnel.
The temperature of the water bath is maintained a t
60 to 65' for 2 to 3 hours until the vigorous evolution of
gas has nearly ceased. As soon as the reaction has been
completed, the separatory funnel is replaced by a
thermometer and the excess thionyl chloride is carefully
recovered by distillation. The acyl chloride is next
distilled over a t 20%209" and collected, rejecting the
first few drops. About 2 ml. of a dark brown liquid
remains in the flask. A yield of 20.7 grams (91 per
cent of the theoretical quantity) of clear, water-white,
o-toluyl chloride boiling at 212" (cor.) is obtained.
Discussion. The excess thionyk-chloride which is
reclaimed upon distillation may be used again in subsequent preparations. Because of the great difference
between the boiling points of thionyl chloride and otoluyl chloride a complete separation is possible.

LITERATURE CITED
CAIIRk, P., AND D. LIBERMANN,
C0mp1. rend., 199, 1422
(1934).
H. T., AND R. R. READ,"Organic Syntheses," Coll.
CLARKE,
Vol. I, John Wiley & Sons, Ino., New York, 1932, p. 500.
CLARKE,
H. T., AND E. R. TAYWR,ibid., Vol. XI, 1931, p. 96.
FIESER,L. F., "ExperimentS in Organic Chemistry," D. C.
Heath & Company, New York, 1935.
L., AND H. WIEIAND,"Labomtory Methods
GAT~ERMANN,
of Organic Chemistry," The Macmillan Company, New
York, 1941.
B. P., AND SAVERIO
ZUFPANTI,
J . Am. Chem. Soc., 57,
GEYER,
1787 (1935).
L.,AND F. F. AHMANN,
ibid., 50,145 (1928).
MCMAWER,

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