254 PROCEEDINGS OP THE AMERICAN ACADEMY 



Constitution of 3IetabromtrimirotoIuol. 



As the metabromtrinitrotoluol is made from the metabromdinitro- 

 toluol, the only point to be determined is the position of the third nitro 

 group ; for this purpose we converted it into the corresponding trini- 

 trotokiidine by treatment with alcoholic ammonia in the cold. The 

 mixture was allowed to stand in a corked flask for about twelve hours ; 

 at first a dark blue color appeared in the liquid, but on longer stand- 

 ing this turned to a deep reddish brown, and a precipitate was de- 

 posited, which with the supernatant liquid at the end of the twelve 

 hours was poured into a dish, and the solvent allowed to evaporate 

 spontaneously. The residue, which was red and yellow, was washed 

 till free from ammonic bromide, and then purified by crystallization 

 from hot glacial acetic acid, until it showed the constant melting point 

 136°, when it was dried at 120°, and analyzed with the following 

 result : — 



0.1144 gr. of the substance gave 24.2 c.c. of nitrogen at a tempera- 

 ture of 23° and a pressure of 754.7 mm. 



Nitrogen 



The melting point of this trinitrotoluidine shows that it is identical 

 with that prepared by Nolting and Sails * by the action of alcoholic 

 ammonia on trinitrometakresolethylether, to which they assign the 

 constitution CH3, NO.,, NHg, NO^, NOg, 1, 2, 3, 4, 6, on the ground 

 that the alcoholic ammonia did not remove any of the nitro groups, 

 and therefore, according to Laubenheimer,t no two of them could be 

 in the ortho position to each other, and this is the only po.ssible ar- 

 rangement in which no two nitro groups are in the ortho position. 

 Our metabromtrinitrotoluol must consequently have the constitution 

 CHg, NO2, Br, NO2, NOo, 1, 2, 3, 4, 6 ; and this conclusion is confirmed 

 by the fact recently discovered in this laboratory,! that the bromtrini- 

 trophenylmalonic ester is converted by boiling with sulphuric acid of 

 specific gravity 1.44 into this metabromtrinitrotoluol melting at 143°. 

 As the bromtrinitrophenylmalonic ester is made from the symmetrical 

 tribromtrinitrobenzol, Br, NO2, Br, NOo, Br, NO^, 1, 2, 3, 4, 5, 6, it 

 can have only the constitution CH(COOC2H5)„, NOo, Br, NO,, NO.^, 



* Ber d. ch. G., xv. 1864. 



t Ber. d. ch. G., ix. 766, 1828. 



t C. Loring Jackson and G. D. Moore. These Proceedings, xxiv. 268. 



