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













Malonic ester 







Chloracetic 

 acid 



Potassium 

 cyanide 



Tempera- 

 ture of 











Theory 



Found 



Per 



No. 



grm. 



grm. 



reaction 

 A 



grm. 



grm. 



cent 



(1) 



200 



175 



110° 



338*8 



264-77 



78*2 



(2) 



200 



165 



110° 



338-8 



295-73 



87-3 



(3) 



200 



165 



90°-95° 



338-8 ' 



293-14 



86-5 



0) 



200 



165 



90°-95° 



338-8 



285-24 



84-2 



(5) 



200 



165 



90°-95° 



B 



90°-95° 



338-8 



295-26 



87*1 



(1) 



200 



165 



338-8 . 



295-76 



87-3 



(2) 



200 



165 



90°-95° 



C 



110° 



338-8 



297*49 



87-8 



(0 



200 



165 



338-8 



296-24 



87-4 



(2) 



200 



165 



90°-95° 



338-8 



292-65 



86-3 



carbonate and extracted the malonic ester with ether. The 

 ether was distilled off, and the ester fractioned under diminished 

 pressure. By recovering and esterifying the acid ester from 

 the sodium carbonate solution, he obtained a weight of malonic 

 ester equal to that of the chloracetic acid employed, or about 

 60 per cent of that theoretically possible. 



In an earlier paper* in this Journal, the best conditions for 

 the esteriiication of malonic acid were studied. In a later 

 paperf a study of the conversion of cyanacetic ester to malonic 

 ester was reported. In preparing material for use in those 

 papers the synthesis from chloracetic acid was employed. It 

 seemed worth while to study these syntheses further and apply 

 the results of the two earlier papers to the practical prepara- 

 tion of malonic ester. This paper reports the results of such 

 a study. 



For the work described in this paper, impure commercial 

 monochloracetic acid was twice fractionally distilled at atmos- 

 pheric pressure, using portions boiling within limits of one to 

 one and one-half degrees. The acid obtained in this manner 

 was found to be about 95 per cent pure as shown by the fol- 

 lowing analyses, made according to Carius: 



I. 0*1808 grm. of acid gave 0*2608 grm. of silver chloride. 

 CI = 35-64 per cent. 

 II. 0-0939 grm. of acid gave 0*1347 grm. of silver chloride. 

 Cl= 35-47 per cent._ 



37*53 per cent. 



Calculated for C 2 H 3 2 C1, CI: 



* This Journal, xxvi, 143. 



f Ibid, xxvi, 257. 



