174 PROCEEDINGS OF THE AMERICAN ACADEMY 



atom of bromine by hydrogen in the dibromdinitrophenylmalouic ester* 

 (which we must infer is an intermediate product in the reaction), and 

 if this replacement is made possible by the presence of the malonic 

 ester radical CH(COOC2ll5)2 in the molecule, we thought that per- 

 haps the two ethoxy radicals in bromdiuitroresorcine diethylether 

 might produce the same effect. The result of the experiment, how- 

 ever, was again negative, whether carried on cold or hot, as the solid 

 product melted at 184° ; and the same result was obtained if acetacetic 

 ester was used instead of malonic ester, although in this latter case the 

 substances were boiled together for four hours. 



Supposing from the negative results of these experiments that the 

 presence of sodium malonic ester as well as malonic ester was neces- 

 sary for the replacement of bromine by hydrogen in the hypothetical 

 dibromdinitrophenylmalouic ester, (leading to an immediate formation 

 of acetylenetetracarbouic ester fas the secondary product,) we tried 

 the action of such a mixture, that is, one molecule of malonic ester 

 to one molecule of sodium malonic ester, upon the bromdiuitroresor- 

 cine diethylether in alcoholic solution, at first in the cold for five 

 days, that is, under the conditions used in the preparation of brom- 

 dinitrophenylmalonic ester, but at the end of this time no sodic 

 bromide could be detected, and essentially all the original ether 

 was recovered unaltered. In another experiment the mixture was 

 heated on the steam bath for fifteen minutes, but, although a dis- 

 tinct red color appeared, the reaction could have been at best a 

 very limited one, as essentially all the bromdiuitroresorcine diethyl- 

 ether was recovered unaltered, so that the new substance, if any 

 were formed, was present in such small quantity that we were un- 

 able to detect it. It follows from these experiments, that the atom 

 of bromine in bromdiuitroresorcine diethylether is more firmly at- 

 tached to the molecule than the second atom of bromine in the 

 hypothetical dibromdinitrophenylmalouic ester, since this is replaced 

 by hydrogen through the agency of malonic and sodium malonic 

 esters, or more probably by the malonic ester alone considering the 

 formation of tartronic acid, t 



Action of Sodic Methylate on Tribromdinitrohenzol. 



We took up this subject because it was possible that the action of 

 sodic methylate might be different from that of sodic ethylate de- 

 scribed in the preceding sections ; but we have found that this is not 



* These Proceedings, xxiv. 239. t Ibid., 2G5. X Ibid., 238. 



