Phelps and Tillotson, Jr. — Malonic Acid or its Ester. 267 



Art. XXIX. — On the Preparation of Malonic Acid or its 

 Ester from Monochloracetic Acid ; by I. K. Phelps and 

 E. W. Tillotson, Jr. 



[Contributions from the Kent Chemical Laboratory of Yale University — 



clxxxv.] 



Kolbe,* starting with chloracetic acid, Mullerf and Finkel- 

 stein^:, with chloracetic ester, and Franchimont§, with brom- 

 acetic ester, have shown that, by acting on the above-named 

 derivatives of acetic acid with potassium cyanide, and subse- 

 quently treating with potassium hydroxide, potassium malo- 

 nate is formed. They give no data showing the yield of 

 malonic acid obtainable under the conditions of experimenta- 

 tion. Yon Miller || treated potassium chloracetate with potas- 

 sium cyanide, boiled with potassium hydroxide, saturated with 

 hydrochloric acid, evaporated to dryness, and extracted with 

 ether. From 100 grm. of monochloracetic acid he obtained 75 

 gnu. of malonic acid, or 70 per cent of that theoretically pos- 

 sible. Conrad^f followed a similar procedure except that 

 instead of evaporating to dryness, he precipitated the calcium 

 malonate. The ester was prepared by saturating a mixture of 

 calcium malonate and absolute alcohol with hydrochloric acid, 

 distilling off the alcohol, washing the ester with a solution of 

 sodium carboDate, and drying over calcium chloride. A yield 

 of 63 per cent of that theoretically possible from the amount 

 of chloracetic acid used was obtained by this method. Grimaux 

 and Tcherneak** and later Bourgoin,ft after acting on sodium 

 or potassium chloracetate with potassium cyanide, saturated 

 the water solution with gaseous hydrochloric acid, evaporated 

 to dryness and extracted the malonic acid with ether. The 

 earlier paper reports a yield of 34 per cent, the later one of 

 64 per cent of the theoretical amount of malonic acid. Claisen 

 and Yenable^ evaporated the aqueous solution of potassium 

 cyanacetate, first obtained, until the temperature reached 135°, 

 pulverized the mass, added alcohol and saturated the mixture 

 with gaseous hydrochloric acid. The product was poured into 

 water, extracted with ether, and the ethereal solution dried 

 over calcium chloride. By this procedure 55 per cent of the 

 theoretical amount of malonic ester was obtained. Noyes§§ 

 treated the pulverized mass of salt, obtained as described above, 

 with a mixture of equal parts of alcohol and sulphuric acid and 

 boiled under a return condenser, added a solution of sodium 



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



% Ann., cxxxiii, 338. § Berichte, vii, 217. 



I Jour, prakt. Chem. [2], xix, 326. ^[Ann., cciv, 121. 



** Bull. Soc. Chim., xxxi, 338. +f Ibid., xxxiii, 572. 



XX Ann., ccxviii, 131. §§ Jour. Am. Chem. Soc, xviii, 1105. 



