Phelps and Tillotson, Jr. — Cyanacetic Ester. 257 



Art. XXVII. — On the Conversion of Cyanacetic Ester to 

 Malonic Ester ; by I. K. Phelps and E. W. Tillotso^, 

 Jr. 



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



Kolbe* and Miillerf, in synthesizing the acids of the oxalic 

 acid series from derivatives of the acetic acid series, note that 

 if cyanacetic acid or its ester is boiled with a concentrated 

 solution of potassium hydroxide, potassium malonate is 

 obtained. This treatment with potassium hydroxide was fol- 

 lowed by FinkelsteinJ, Franchimont§, Yon Miller] and Con- 

 radT, but in no case were the quantities obtained given. Van't 

 HofT**, starting with cyanacetic acid, states that the yield of 

 malonic acid obtained by this process is eighty per cent of that 

 theoretically possible. He explains the loss as due to decom- 

 position according to this equation : 



CH 2 (COOK) 9 + KOH = CH 3 COOK + K 2 C0 3 . 



Franchmiontft and Yan't Hoffff both give it as their opinion 

 that a better yield may be obtained by the use of hydrochloric 

 acid in the place of potassium hydroxide as a hydrolizing 

 agent. Hydrochloric acid was apparently first made use of 

 for the purpose of converting cyanacetic acid to malonic acid 

 by Grimaux and Tchierneak^, later by Bourgoin§§, and by 

 Claisen and Venable||||. NoyesTfTf employed sulphuric acid in 

 the presence of chlorides to effect the same conversion, but in 

 none of the instances cited were the quantities obtained given 

 to show the amount of malonic acid or ester obtainable from 

 a given amount of cyanacetic acid or ester. 



For the work here recorded, cyanacetic ester was made by 

 esterifying the acid obtained by acting on chloracetic acid with 

 potassium cyanide under conditions which will be given in a 

 later paper. The cyanacetic ester, synthesized in this way, 

 was fractionally distilled at atmospheric pressure with a Hem- 

 pel bead column of the particular form described in a former 

 paper*** in this Journal. The portions boiling within limits of 

 four-tenths of a degree, 205-6°-206° (corrected), were used in 

 all the experiments of series A in Tables I and II. During 

 the distillation under atmospheric pressure, the ester in the 

 flask assumed a deep red color, gradually depositing a small 



* Ann., cxxxi, 348. f Ann., cxxxi, 350. 



X Ann., cxxxiii, 338. gBerichte, vii, 217. 



|| Jour. Prakt. Chem. [2], xix, 326. U Berichte, xii, 749. 



**Berichte, vii, 1382. ffLoc. cit. 



#Bull. Soc. Chim., xxxi, 338. §§Comptes Rendus, xc, 1289. 



HI Ann., ccxviii, 131. ^[Jour. Am. Chem. Soc., xviii, 1105. 



***This Journal, xxvi, 243. 



