4-Amino-2,6-Dinitrotoluene → 2,4,6-Trinitrotoluene

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Reaction Steps

An alternate method of pentanitroaniline synthesis, based on a recent patent (Reference 6), was examined (FIG. 4). 2,4,6-trinitrotoluene (TNT) (10) is dissolved in p-dioxane and H2S gas is bubbled through the solution holding the temperature below 50° C. The sulfur which precipitates is filtered off and the filtrate is poured over ice mixed with water to produce a mixture of the desired intermediate 4-amino-2,6-dinitrotoluene (11) and the partially reduced product 2,6-dinitro-4-hydroxylaminotoluene (12); the ratio of 11:12 usually is 3:2, but varies from 1:2 to 2:1. The crude mixture of 11 and 12 is suspended in hydrochloric acid and treated with potassium iodide. The hydrochloric acid and potassium iodide form hydroiodic acid (HI) which serves as the reducing agent to convert the hydroxylamine 12 into the amine 11. Cooling, filtration, and recrystallization provide the desired 11 in 45% overall yield from TNT. The amine 11 is nitrated using concentrated sulfuric acid/90% nitric acid with heating to 80° C. (Under these nitration conditions, the methyl group on the amine is oxidized, carbon dioxide is liberated, and subsequent nitration occurs at this position on the aromatic ring.) The nitrated mixture is allowed to cool to 60° C. and then extracted with dichloroethane. The extract is dried and concentrated to produce pentanitroaniline (9) in 22% yield (10% overall yield from TNT).

Provenance & Evidence