Synthesis of l,3,5-triamino-2,4,6-trinitrobenzene TATB

All reported syntheses of TATB to date involve the nitration of substrates containing leaving groups which are subsequently replaced by amino groups. The current industrial synthesis of TATB (14) involves the nitration of 1,3,5-trichlorobenzene (33) to 1,3,5-trichloro-2,4,6-trinitrobenzene (34) followed by reaction with ammonia in toluene under pressure. Both nitration and amination steps require forced conditions with elevated temperatures. 

The tri-nitration of 3,5-dichloroanisole (134) followed by ammonolysis of the product (135) with ammonia is a much more facile route to TATB (14) although the cost and availability of (134) makes this route of academic interest only.  

The tri-nitration of 1,3-dimethoxybenzene with mixed acid, followed by amination, is a patented route to DATB. A similar route to TATB employing 1,3,5-trimethoxybenzene and dinitrogen pentoxide only results in moderate yields.  

The synthesis of TATB (14) from the reaction of 2,3,4,5,6-pentanitroaniline (31) with ammonia has been reported. In one route, 2,3,4,5,6-pentanitroaniline (31) is synthesized from the nitration of 3,5-dinitroaniline (30) the latter is obtained from the selective reduction of TNB ° or via a Schmidt reaction with 3,5-dinitrobenzoic acid. Another route to 2,3,4,5,6-pentanitroaniline (31) involves the selective reduction of TNT (1) with hydrogen sulfide in ammonia followed by nitration of the resulting 4-amino-2,6-dinitrotoluene (46), during which the methyl group is lost by oxidation-decarboxylation. 

Recently, TATB (14) has been synthesized by treating TNB and picramide (53) with VNS aminating agents like 4-amino-1,2,4-triazole (ATA) and 1,1,1-trimethylhydrazinium iodide (TMHI) in the presence of sodium methoxide in Hydroxylamine has been used 

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