Phelps and Tillotson, Jr. — Cyanacetic Ester. 263 



is added as such, in which case sufficient water is formed in a 

 secondary reaction or else the ortho ester first formed is decora- 

 posed into the normal ester and ethyl ether. High yields may 

 be obtained without the use of a catalyzer other than the 

 hydrochloric acid with which the solution was saturated, but by 

 the use of an additional catalyzer as ziuc chloride, or prefer- 

 ably sulphuric acid, nearly theoretical yields of malonic ester 

 result. In experiment .(7) of series A and (1) of series B in 

 Table II, if the loss of 4- 2 per cent sustained by the treat- 

 ment and the recovery of the malonic ester, in the amount used 

 here and under these conditions, is considered, it seems prob- 

 able that the conditions named above are those under which 

 conversion of ethyl cyanacetate to ethyl malonate is complete. 

 The best results were obtained when 50 grm. of cyanacetic ester 

 with 125 cm3 of absolute alcohol and 4 grm. of sulphuric acid, 

 cooled in a mixture of ice and salt, were thoroughly saturated 

 with hydrochloric acid by passing in a stream of dry hydro- 

 chloric acid for four hours, the resulting mixture being esterified 

 during a period of two hours, at 100°-110°, with 200 cm3 of abso- 

 lute alcohol. Under these conditions the yield actually 

 obtained was 96*3 per cent of that theoretically possible. 



