258 Phelps and Tillotson, Jr. — Cyanacetic Ester. 



amount of a reddish-brown insoluble substance. The ester 

 obtained in this manner gave the following analyses : 



I. 0*3252 grm. of ester gave 30*5 cmS of moist nitrogen at 24° and 

 758-2 mm . N = 10-48 per cent. 

 II. 0-4891 grm. of ester gave 45'8 cm3 of moist nitrogen at 25° and 

 774 mm . N = 10-45 per cent. 



Calculated for C 5 H 7 2 N, N = 12-40 per cent. 



For the experiments in series B of Tables I and II the cyan- 

 acetic ester was fractionally distilled under diminished pres- 

 sure and was proved by the following analyses to be pure : 



I. 05020 grm. of ester gave 55*3 cm3 of moist nitrogen at 23° and 

 763'2 mm . K = 12-47 per cent. 

 II. 0*5004 grm. of ester gave 55 emS of moist nitrogen at 20° and 

 758-2 mm . N = 12*54 per cent. 

 Calculated for C 6 H 7 2 N, N = 12-40 per cent. 



The alcohol used in all the experiments recorded was made 

 as free as possible from water by repeated distillations from 

 calcium oxide. Zinc chloride of commerce was freshly fused 

 for use in the experiments of Table I. In the experiments of 

 Table II sulphuric acid of commerce, sp. gr. 1*84, was employed. 



In all the experiments in Tables I and II, except those in 

 which the treatment was special, 50 grm. of cyanacetic ester, con- 

 tained in a 500 cm3 round-bottomed flask, together with definite 

 amounts of absolute alcohol, zinc chloride or sulphuric acid, 

 and with or without definite amounts of water, as shown in 

 the tables, were saturated with gaseous hydrochloric acid, dried 

 by passing through a wash bottle containing concentrated sul- 

 phuric acid, keeping the solution cooled in a mixture of ice 

 and salt. While the current of hydrochloric acid was still 

 flowing, the ice mixture was replaced by means of a water 

 bath, and the solution heated to the boiling point of the alco- 

 hol under a reflux condenser for an additional period of time, 

 as shown in the tables. 



The ammonium chloride was filtered off and washed with 

 absolute alcohol or ether. The filtrate was then treated in the 

 special arrangement of flasks for esterification described in a 

 former paper* in this Journal. For this treatment, 200 cm3 of 

 absolute alcohol was distilled from the reservoir flask through 

 a period of one and one-half to two hours. The crude product 

 so obtained was transferred to a separating funnel containing 

 chipped ice, an excess of sodium carbonate solution added to 

 neutralize any free acid present, and the whole shaken out 

 with ether. The ethereal solution was washed with water 

 containing sodium chloride, and the carbonate and chloride 



* This Journal, xxiv, 194. 



