372 



Interaction of ammonia and amines. 



As appears from the often-quoted paper, the intei-action of methyl- 

 amine. which is dependent on the conditions prevailing during the 

 experiment gives rise to different resuUs. Not merely one nitro-group 

 of the nucleus may be substituted, but in addition also the methyl- 

 nitraminogroup. It now seemed not without interest to repeat these 

 reactions not only with ammonia, brtt also with some other amines, 

 aliphatic as well as aromatic ones. Before stating the results obtained 

 it may be mentioned briefly what is already known as to the inter- 

 action of ammonia and amines on the alkylnitramino-group of aromatic 

 nitramines. 



Picrylmethylnitramine, according to v. Romburgh and Maurenbrecher^) 

 reacts with ammonia, with aliphatic as well as with aromatic amines 

 — such as aniline, paratoluidine etc. — in such a manner that in 

 addition to picramide (substituted picramide respectively) methyl 

 nitramine is formed. 



In an analogous manner, using paratoluidine, both methylnitra- 

 mino-groups in 2.4.6-trinitromelaphenylenedimethylnitramine become 

 substituted. 



Sommer') allowed ammonia and different amines — aliphatic as 

 well as aromatic — to act on 2.3.()-trinitro 4 tolylmethylnitramine 

 which caused the nitro-group in the position 3 to be substituted. 

 Methylamine also reacted on the nitramino-group. With ammonia, 

 methyl- and dimethylamine it was necessary to work at 100° under 

 pressure as no reaction took place at the ordinary temperature. 

 When we allowed ammonia and different amines to react on the 

 tetranitrophenylmethylnitraraine we obtained reactions analogous to 

 the action of methylamine. Ammonia, however, reacted slower than 

 the amines. 



An exception was noticed in the case of diz's'opropylamine, under 

 the influence of which tlie nitro-group in the position 3 is replaced 

 by OH. It then yields with the phenol the di/.s-opropylamine salt. 



The aromatic amines, aniline and paratoluidine act on the mova- 

 ble nitro-group only, even in heating. 



Piperidine also acted abnormally, the piperidine salt of tetranitro- 

 methylnitraminophenol was formed. 



Highly peculiar was the interaction of pyridine and chinoline 

 which, although quite dry, gave salts of the trinitromethylnilramino- 

 phenol while simultaneously an evolution of gas (ook place. 



1) Proc Roy. Akad. Amst. IX, 704 (1907). 

 J f. Pr. Ch. 67, 513 (1903). 



