Reactions of N-Acyloxy-2-nitrobenzenamines. I. Thermolysis in Benzene or Bromobenzene

Abstract

N-Acyloxy-2-nitro- and N-acyloxy-2,4-dinitro-benzenamines have been pyrolysed at 140º in benzene or bromobenzene solution. Homolysis (to form RCO₂ and ArNH ) is ruled out since virtually all the carboxylate is isolated as carboxylic acid. This acid might arise via a concerted elimination process (the other product being a benzofurazan 1-oxide), or via heterolysis to ArNH⁺, RCO₂- with subsequent transfer of proton, and cyclization of the singlet 2-nitrophenylnitrene. These simple reactions compete with bimolecuiar reactions of products with substrate, in which the corresponding amine, azoxy compound and acid anhydride are generated.

Attempts to synthesize N-tosyloxy derivatives of nitrobenzenamines gave only thermal decomposition products. N-Trifluoroacetoxy-2,4-dinitrobenzenamine was isolated as a crude product which detonated violently.