276 Phelps and TiUotson, Jr. — Cyanacetic Acid. 



Cyanacetic ester 



Chlorace- Potassium Temperature , ' N 



tic acid cyanide of reaction Theory Found 



No. grm. grm. grm. grm. Per cent. 



A 



(1) 200 165 90°-95° 239*4 219*78 91*4 



(2) 200 165 110° 239-4 224*15 93*6 



(3) 200 165 110° 239*4 222-00 92*7 



(4) 200 165 110° 239*4 220*00 91*9 



B 



(1) 200 165 0°-5° 2.39*4 213*30 89\L 



(2) 200 165 90°-95° 239*4 218*72 91*4 



(3) 200 165 90°-95° 239*4 220*04 91*9 



(4) 200 165 110° 239*4 207*68 86*8 



(5) 200 165 110° 239*4 206*63 85*1 



cyanide react in alkaline solution at 100° to form the theoreti- 

 cal amount of sodium cyanacetate. The work recorded in 

 this paper is a study of the formation of ethyl cyanacetate 

 from monochloracetic acid, making use of the best conditions 

 for the esteriiication of cyanacetic acid as described in an 

 earlier paper* in this Journal. 



For the work described in this paper the impure monochlor- 

 acetic acid of commerce was fractionally distilled twice at 

 atmospheric pressure, using portions boiling within limits of 

 one and one-half degrees. The acid so obtained was found, by 

 analysis given in a former paper,*)* to be about 95 per cent pure. 

 Commercial potassium cyanide of 96-98 per cent purity was 

 used in all the experiments. The alcohol employed in esteri- 

 iication of the cyanacetic acid was made as free as possible 

 from water by repeated distillations from calcium oxide. 



In all the experiments except those in which the treatment 

 was special, 200 grm. of monochloracetic acid of the purity 

 described above, was treated in a liter flask with about 300 

 grm. of hydrous sodium carbonate and 50 cm3 of water to start 

 the reaction. The temperature of the mass usually became so 

 low that the mixture was frozen. The action may be hastened 

 by immersing the flask in water at room temperature. Good 

 results were also obtained by using about 110 grm. of anhy- 

 drous sodium carbonate* and 250 cm3 of water, but since the 

 reaction with the hydrous carbonate takes place with cooling, 

 there is less tendency towards hydrolysis of the chloracetate. 

 The alkaline solution of sodium chloracetate was then poured 

 into a hot solution of 165 grm. of potassium cyanide in 250 cm3 

 of water and after the action had taken place the solution was 

 boiled for five minutes to complete the reaction. To the 

 cooled solution was then added sulphuric acid in slight excess, 



* This Journal, xxvi, 264. f This Journal, xxvi, 268. 



