
%0 Journal Article
%A Bryant, IR 
%A Dyall, LK 
%T Reactions of N-Acyloxy-2-nitrobenzenamines. I. Thermolysis in Benzene or Bromobenzene
%J Australian Journal of Chemistry
%D 1989/12/01
%V 42
%N 12
%P 2275-2288
%K 
%R https://doi.org/10.1071/CH9892275
%U https://www.publish.csiro.au/paper/CH9892275 
%X 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. 
