Molecular rearrangements, part 33, photolysis and thermolysis of arylnitramines

Abstract

Ultraviolet irradiation of arylnitramines in 2,6-di- tert-butylphenol results in the transfer of the nitro group intermolecularly to produce the corresponding 4-nitrophenol together with nitroanilines in addition to oxidation products, diphenoquinone and the diphenolic compounds. Thermolysis of arylnitramines or N-alkylarylnitramines at controlled temperatures either alone or in phenolic solvent, produce the corresponding p- and/or o-nitroanilines together with 4-nitrophenol, diphenoquinone and diphenol in addition to crystals of their dimeric product quinhydrone. No dimerization products of the arylamino radicals are detected. However, evolution of nitrogen, nitrogen dioxide and water drops are detected. Thermolysis of primary arylnitramines in β-naphthol results in separation of free radicals substitution product, 1-arylazo-2-naphthols as major products with evolution of nitrogen dioxide. However, such rearrangement products are not produced with secondary N-alkylarylnitramines. Other products of homolytic substitution of halogen by nitro group are identified.