260 Phelps and TiUotson, Jr. — Cyanacetic Ester. 



added to dissolve the ammonium chloride and the ester was 

 recovered directly in the manner described above. In experi- 

 ments (4) of series A, (1) of series B of Table I, (7) of series 

 A and (1) of series B of Table II, after saturation with hydro- 

 chloric acid in the cold, the solution was treated directly in 

 the esterification apparatus, the ammonium chloride being 

 precipitated when the temperature had reached 60°-70° dur- 

 ing the process of esterification. In experiment (5) of series 

 A of Table I, after saturating in the cold with hydrochloric 

 acid, the excess of hydrochloric acid, alcohol, water and all 

 low-boiling products were removed by heating the flask in a 

 water bath at 50° under diminished pressure, and the 

 remainder was esterified in the usual manner. In this experi- 

 ment, no considerable amount of ammonium chloride was pre- 

 cipitated, and there remained in the distillation flask a viscous 

 fluid which did not distil with the malonic ester and which 

 began to decompose on being heated to a higher temperature. 

 In experiment (1) of series A of Table II, cyanacetic ester was 

 boiled with alcohol sp. gr. 0*825 and sulphuric acid sp. gr. 1*84: 

 under a return condenser for two hours, and as no ammonium 

 salt was precipitated, gaseous hydrochloric acid was passed in 

 for three hours, the ammonium salt filtered off, and the pro- 

 cess continued in the usual manner. 



The theory for malonic ester given in series A of Tables I 

 and II was calculated on the basis of the analyses of the first 

 sample of ester, given above, and with the assumption that 

 the substance was a mixture of cyanacetic and malonic esters. 

 This assumption was apparently justified, first, by the fact 

 that, on treatment, it yielded pure malonic ester, and second, 

 on saponification, a mixture of cyanacetic and malonic acids 

 was obtained. It was further assumed that all fractions pre- 

 pared in the same way and boiling at the same temperature, 

 205'6°-206° (corrected), had the same composition. Experi- 

 ments (7) and (8) of series A of Table II were made using 

 portions of the samples analyzed. The theory given in series 

 B of both tables was calculated on the basis of pure ethyl 

 cyan acetate. This is presumed to be justified by the analyses 

 given above as well as by the yields of malonic ester obtained 

 from it. 



The loss sustained by saturating an alcoholic solution of 

 malonic ester with hydrochloric acid was determined by a 

 blank test. When 75 grm. of pure ethyl malonate, with 125 cm3 

 of absolute alcohol was saturated with hydrochloric acid for 

 the same time and under the same conditions as in the several 

 experiments, 72*02 grm. were recovered, with a loss of 2*98 

 grm. or 4*2 per cent. This loss must be added to the results 

 given in the table in order to show the extent "of the conver- 



