481
R-COOH
+ SOCl*
-r
R-COCl
+
+ HCl (a) ++ SO* (a)
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,