W. A. Drushel — Hydrolysis of Esters in Fatty Acids, 31 



stages. The first reaction proceeded too rapidly to make accu- 

 rate velocity measurements, having reached an equilibrium in 

 from five to ten minutes with a loss in the alkalinity of the 

 solution nearly equivalent to the concentration of ester used. 

 No apparent formation of ammonia occurred in this first reac- 

 tion and it no doubt resulted only in the liberation of alcohol 

 and the formation of basic or neutral barium cyanacetate accord- 

 ing to the equations : 



CN-CH-COOCH+Ba(OH) 2 > 



CN-CH 2 -COO-Ba-OH + C 2 H-OH, or 

 2CN-CH -COOCH + Ba(OH) — ^ 



(CN-CH 2 -COO-) 2 Ba + 2C 2 H-OH 



Several hours after the alkalinity of the reaction mixture 

 had reached an equilibrium the presence of ammonia became 

 apparent and clusters of needle-shaped crystals began to 

 deposit on the walls of the flasks containing the reaction mix- 

 tures. This reaction continued for several days at 35° C. and 

 for more than two weeks at 25° C. with an increase in the 

 amount of crystalline product and ammonia without any 

 increase in the alkalinity of the reaction mixture. This reac- 

 tion evidently consists of the hydrolysis of the cyanogen group 

 with the formation of free ammonia and barium malonate 

 according to the following equation : 



CN-CH 2 -COO-Ba-OH + HOH >Ba(COO) 2 CH 2 + NH 3 . 



The crystalline salt formed in this reaction on analysis 

 proved to be barium malonate. 



Summary. — When ethyl cyanacetate is hydrolyzed in deci- 

 normal aqueous hydrochloric acid the rate of hydrolysis is 

 much lower than that of ethyl monochloracetate under the 

 same conditions, the effect of the replacement of hydrogen by 

 cyanogen in the acetyl group being a much greater depression 

 of the velocity of hydrolysis than would be expected from the 

 strength of the cyanetic acid generated in the reaction". In. 

 water alone the hydrolysis of ethyl cyanacetate also proceeds 

 more slowly than the hydrolysis of ethyl monochloracetate 

 although cyanacetate acid is more strongly dissociated than 

 monochloracetic acid. This marked retardation in the hydrol- 

 ysis reaction in the presence of the cyanogen group may be 

 due to an effect analogous to what in the esterification reaction 

 is called steric hindrance, or the possibility of the existence of 

 polymerized molecules of cyanacetic ester in aqueous solution 

 may be suggested as an explanation of the retarded action. 



In alkaline solution the hydrolysis of ethyl cyanacetate pro- 

 ceeds in two stages. The first is a very rapid decomposition 

 of the ester into alcohol and the alkali cyanacetate, and the 

 second is the hydrolysis of the alkali cyanacetate to the alkali 

 malonate and ammonia. 



