240 PROCEEDINGS OP THE AMERICAN ACADEMY 



III. C 6 HBr 2 (N0 2 ) 2 CNa(COOC 2 H s ) 2 + CH 2 (COOC a H 5 ) 2 = 



C e H 2 Br(N0 2 ) 2 CNa(COOC 2 H 5 ) 2 + CHBr(COOC 2 H 5 ) 2 . 



IV.. NaCH(COOC 2 H 5 ) 2 + H 2 = NaOH + CH 2 (COOC 2 H 5 ) 2 . 

 V. CHBr(COOC 2 H 5 ) 2 + NaOH = CHOH(COOC 2 H 5 ) 2 + NaBr. 



Of these reactions, I., II., and III. take place before, IV. and V. 

 after, the addition of the water used in working up the product. That 

 Reaction III. takes place we infer from our discovery of tartronic i cid 

 among the products of saponification of the oil, as Conrad and Bischoff * 

 have proved that brommalonic ester is decomposed by sodic hydrate, 

 according to Reaction V.f 



The experiments of one of us with G. D. Moore upon the action 

 of sodium malonic ester on tribromtrinitrobenzol have shown that 

 these reactions take place in a way analogous to that just worked out. 

 For the details we would refer to the paper on this subject. 



The objection which might be raised against these reactions, that 

 the yield of bromdinitrophenylmalonic ester is at best only about 50 

 per cent of that required by theory, and therefore that some other 

 substance may be formed from the tribromdinitrobenzol in addition to 

 it, is disposed of by the fact that on making the dibromdinitrophenyl- 

 malonic ester from tetrabromdinitrobenzol by exactly analogous re- 

 actions, the yield rose to 80 per cent of the theoretical. t It follows, 

 therefore, that the 47 to 50 per cent unaccounted for in our preparations 

 remained dissolved in the oily secondary product ; but although we 

 have made many attempts to recover it, none of them have been 

 crowned with success. 



The absence of malonic acid in the product of the action of hydro- 

 chloric acid on the oil seems to us extraordinary, as we purposely kept 

 the temperature of the saponification at 130°, in order to avoid decom- 

 posing the malonic acid, which we expected from the excess of malonic 

 ester undoubtedly present in the oil. We can account for this only 

 by supposing that malonic acid is decomposed in presence of strong 

 hydrochloric acid at a lower temperature than when heated alone. 



Saponification of Bromdinitrophenylmalonic Ester- 



In our previous paper we stated that strong hydrochloric acid de- 

 composed bromdinitrophenylmalonic ester, when the two substances 



* Ann. Chetn., ccix. 222. 



t A fuller discussion of these reactions will be found in the general paper at 

 the end of this series. 



t These Proceedings, xxiv. 295. 



