Synthetic Utilization of Polynitroaromatic Compounds. 1. S-Derivatization of 1-Substituted 2,4,6-Trinitrobenzenes with Thiols

Abstract

Reactions of 1-R-2,4,6-trinitrobenenes (R = alkyl, protected aldehyde, aminocarbonyl, cyano groups, or isoxazole ring) with thiol salts were investigated. In most cases, these reactions gave a mixture of minor para and major ortho substitution products. Reactions of N,N-disubstituted 2,4,6-trinitrobenzamides with S-,O-, and N-nucleophiles afforded products of substitution of the p-nitro group exclusively. 1-Cyano-2,4,6-trinitrobenzene was found to be the most reactive and the least selective: all three nitro groups can be substituted using an excess of thiol salts. 2-R-4, 6-dinitrobenzamides showed no regioselectivity under similar conditions to yield 1:1 mixtures of para and ortho isomers.

Synthesis of substituted dibenz[b,f]oxepines from 2,4,6-trinitrotoluene

“…2 [(4 Methylphenyl) sulfanyl] 4,6 dinitrotoluene 3 was synthesized from 2,4,6 tri nitrotoluene according to a known procedure. 10 The X ray diffraction data for compound 2a (C 20 H 13 NO 4 ) were measured at -173 °C on an automated three circle Smart APEX II CCD diffractometer (Mo Kα, graphite monochro mator, ω scanning technique, 2θ < 60°). At -173 °C, the crystals are monoclinic: a The structure of 2a was solved by direct methods and refined by the full matrix least squares method with anisotropic dis placement parameters.…”

Synthesis of benzannelated five-membered heteroaromatic compounds from 2,4,6-trinitrotoluene

“…6 The treatment of the intermediate acid with SOCl 2 (or PCl 5 ) leads to respective acid chloride, and the latter reacts with aqueous ammonia solution to give 2,4,6-trinitrobenzoic acid amide. 7 Another approach to preparing the amide is a reaction of 2,4,6-trinitrobenzoic acid with urea. The reaction runs in 30% oleum.…”

“…The reaction runs in 30% oleum. 7 Such method allows preparing the amide in a higher yield (90%) than by the acid chloride treatment with NH 3 (58%).…”

Chemical Conversion of TNT: Production of 2,4,6-Trinitrobenzoic Acid

“…[1][2][3][4] However, until now, there has been no satisfactory procedure for preparing TNBA, which can be a basis for industrial production of this compound. 2,4,6-Trinitrotoluene (TNT) is a plentiful, available starting material for the production of TNBA by oxidation in strongly acidic media.…”