Aromatic nitramines

Numerous aromatic nitramines have been synthesized but only A,2,4,6-tetranitro-A-methylaniline (tetryl) and l-(2-nitroxyethylnitramino)-2,4,6-trinitrobenzene (pentryl) have found practical use as explosives. Both tetryl and pentryl are more powerful than TNT. Tetryl is widely used in boosters and as a component of explosive formulations like tetrytol (tetryl/TNT), PTX-1 (tetryl/RDX/TNT) and Composition C-3 (tetryl/RDX/TNT/DNT/MNT/NC). 

Tetryl (8) can be prepared from the nitration-oxidation of A, A-dimethylaniline (90) with a variety of nitrating agents and conditions, including the use of a large excess of 70 % nitric 

Tetryl (8) can be synthesized in two steps from 2,4-dinitrochlorobenzene (231). Thus, reaction of the latter with methylamine under aqueous conditions yields 2,4-dinitro-lV-methylaniline (228), which readily undergoes nitration to tetryl (8) on treatment with mixed 

Tetryl has been synthesized by treating picryl chloride with the potassium salt of methyl-nitramine but the reaction is of theoretical interest only.  

Pentryl (152) is obtained from the action of fuming nitric acid or mixed acid on Ai-(2,4-dinitrophenyl)ethanolamine, itself obtained from the reaction of 2,4-dinitrochlorobenzene with ethanolamine. Another route to pentryl (152) involves the nitration of A-phenylethanol-amine, which is obtained from the reaction of aniline with ethylene oxide.  

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Other aromatic nitramines have not found use as practical explosives. Ethyltetryl (232) is prepared from the nitration of 2,4-dinitro-A-ethylaniline, A,A-diethylaniline or N-ethylaniline. Butyltetryl (233) can be synthesized from the nitration of 2,4-dinitro-A-butylaniline, which is attainable from the reaction of n-butylamine with 2,4-dinitrochlorobenzene. 

The aromatic nitramine (234) can be prepared by nitratingA, A -diphenylethylenediamine ° or 2,2, 4,4 -tetranitro-A,A -diphenylethylenediamine with mixed acid, the latter synthesized from 2,4-dinitrochlorobenzene. The azoxy-nitramine (235) is prepared by nitrating 4,4 -bis(dimethylamino)azoxybenzene with mixed acid. ... 

Bratin, K., P. T. Kissinger, R. Briner, and C. Bruntlett. Determination of nitro aromatic, nitramine, and nitrate ester explosive compounds in explosives mixtures and... 

Rearrangement of primary and secondary aromatic nitramines occurs in an acid medium with the formation of C-substituted aniline derivatives (Bamberger and Landsteiner [17]). 

The reaction of primary aromatic nitramines with nitrous acid is specific and leads to the formation of diazonium nitrate (Bamberger [23]). According to Stevens [24] this reaction is also a kind of reduction, and presumably may be represented as follows ... 

The key representative of aromatic nitramines is the trinitro derivative of phenyl-methylnitramine—tetryl. This is 2,4,6-trinitrophenyhnethylnitramineorpicrylmethyl-nitramine or N-2,4,6-tetranitro-N-methylaniline. 

After this, van Romburgh worked with aromatic nitramines while Franchimont(first alone and then with Klobbie and van Erp) studied aliphatic nitramines. Considerable work was done, beginning about 1890, in Germany and in Italy. In Istcf y 2r j ork on nit rain incs was conducted not only in Holland and Germany but in other countries as well. Great advances were made during and after WW II, particularly in the USA (where most of the work is stiii classified) in Canada(where many papers have been published in Canad jRes and JCS) and in Russia... 

Aromatic nitramines-are much easier to prepare than the aliphatic nitramines. For this, the aromatic amine can be treated with coned nitric acid either alone or in the presence of a dehydrating agent such as sulfuric acid or acetic acid-acetic anhydride(Ref 2, n... 

Franchimont, Rec 16,226 8(1897) (Contribution to the knowledge of aliphatic nitramines) b) J.Pinnow, Ber 30,833-43(1897) (Aromatic nitramines and nitrosamines) c)E.Bamberger, J3er 30,1248-63(1897) (AIkylnitramines)(earlier refs are given) d)G.R.Ciemo j.M.Smith,... 

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