264 Phelps and Tillotson, Jr. — Cyanacetic Acid. 



Art. XXYIII. — -Researches on the Influence of Catalytic 

 Agents in Ester Formation . On the Esterification of Cyana- 

 cetic Acid ; by I. K. Phelps and E. W. Tillotson, Jr. 



[Contributions from the Kent Chemical Laboratory of Yale Univ. — clxxxiv.] 



Yan't Hoff* states that cyanacetic ester may be obtained 

 by dissolving cyanacetic acid in alcohol, saturating with hydro- 

 chloric acid gas, pouring the mixture into water and extract- 

 ing w T ith ether, but he gives no data concerning the amount 

 of ester to be obtained from a known amount of cyanacetic 

 acid. In former papersf from this laboratory there have been 

 shown the effects produced upon esterification of succinic, 

 benzoic and malonic acids by varying the proportion of the 

 reagents, the catalyzers and the time of reaction. In this 

 paper is recorded a similar study w T ith cyanacetic acid. 



Cyanacetic ester was prepared from chloracetic acid under 

 conditions which will be described in a later paper. The ester 

 boiling within four-tenths of a degree, was converted to the 

 acid by heating with double its volume of water and a few 

 drops of nitric acid, at a temperature of about 60°, for some 

 time after the mixture had become homogeneous. The solu- 

 tion was then evaporated at a temperature of 60° till the point 

 of saturation was reached and the crystals which separated on 

 cooling were recrystallized from a mixture of ether and chloro- 

 form. The acid so obtained was in the form of very fine, 

 perfectly white, hygroscopic crystals, melting at 66*1 -66*4° 

 (corrected). 



Cyana- 



No. cetic 



acid ZnCl 2 H 2 S0 4 



0) 

 (2) 

 (3) 

 (4) 



(5) 



(6) 



0) 



(8) 



*Berichte, vii, 1382. 



Table I. 



Alcohol 

 with HC1 



Time 



Cyanacetic ester 



Theory Found 

 per cent hr. min. 



"'■ 1 5 



l' 25 1 10 

 1-25 



1>25 1 10 

 1-25 



1-25 



1-25 l I 5 



1*25 



1-25 -" 



"- 1 10 

 ""I 5 



9 TO 



160 

 f This Journal, xxiv, 194 ; xxv 



grm. 



grm. 



grm. 



cm 3 per cent hr. 



min. 



grm. 



grm. Per cent 



50 



-- 



-- 



40 



160 



1 



5 



66-47 



42-19 



63-5 



50 



-- 



-- 



40 

 160 



1-25 

 125 



10 



66-47 



58-92 



88-6 



50 



1 



-- 



40 



160 



1-25 

 1-25 



10 



66-47 



59-69 



89-8 



50 



10 



-- 



40 

 160 



1-25 

 1-25 



5 

 t 



66*47 



63-18 



95-1 



50 



10 



-- 



40 

 160 



1*25 

 1-25 



-- 



66-47 



55-53 



83-5 



50 



-- 



0-5 



40 

 160 



1 



10 



66-47 



62-68 



94-3 



50 



-- 



2-0 



40 

 160 



— 1 



5 



66-47 



64-20 



96-6 



50 





2-0 



40 



"-- 2 



10 



66-47 



64-52 



97-1 



; xxvi, 143. 



