The chemistry of 2,4,6-trinitrotoluene TNT

The acidity of the methyl group in TNT is illustrated by its ability to participate in Mannich-type reactions in the same role as a ketone, the methyl group of TNT behaves as a nucleophile 

The methyl group of TNT will condense with aldehydes in a similar way to other substrates containing acidic protons. TNT (1) reacts exothermically with benzaldehyde in alkaline solution to form 2,4,6-trinitrostilbene (140). 2,4,6-Trinitrobenzaldehyde (142) is synthesized from the base hydrolysis of the imine (141) formed from the condensation of TNT (1) with /t-nitroso-N,N-dimethylaniline.  

A synthetically important route to 1,3,5-trinitrobenzene on both laboratory and industrial scales utilizes TNT as a starting material. Thus, when TNT (1) is treated with an oxidizing mixture of sulfuric acid and sodium dichromate the product formed is 1,3,5-trinitrobenzoic acid (144), which is thermally unstable and loses carbon dioxide on heating as a suspension in boiling water to form 1,3,5-trinitrobenzene (2). ° 

6-Trinitrobenzyl chloride is isolated in 85 % yield if a reaction mixture composed of TNT and 5 % aqueous sodium hypochlorite in methanol at 0 °C is quenched into dilute acid after 1 minute longer reaction times at ambient temperature lead to the isolation of the heat resistant explosive 2,2, 4,4, 6,6 -hexanitrostilbene (HNS) in 42 % yield. HNS (16) is also formed in 50 % yield from the reaction of 2,4,6-trinitrobenzyl chloride (145) with sodium hydroxide in THF-methanol. Sollot ° later found that the yield of 2,2, 4,4, 6,6 -hexanitrostilbene (16) could be increased to 70 % by treating the same substrate with 2.4 mole equivalents of triethylamine in the same solvent mixture. 

TNT has been used as a starting material for the synthesis of 2,3,4,5,6-pentani-troaniline (see Section 4.8.4), and hence, for the synthesis of hexanitrobenzene via oxidation with peroxydisulfuric acid, and l,3,5-triamino-2,4,6-trinitrobenzene (TATB) via nucleophilic displacement with ammonia.  

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