Molecular rearrangements. VII. N-alkylarylamines (III). Thermal rearrangement of secondary arylamines.

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Heating of N-benzyl-o- and p-toluidines resulted in migration of the benzyl group to the corresponding toluidine nucleus. The pyrolysis of N-benzyl-o-toluidine produced ammonia, toluene, bibenzyl, trans-stilbene, o-toluidine together with 4-amino-3-methyldiphenylmethane and 2,3-diphenyl-7-methylindole. N-benzyl-p-toluidine resulted into the same neutral products together with ammonia, p-toluidine, 2,3-diphenyl-5-methylindole together with 2,7-dimethyl-9-phenylacridine. Using phenol or quinoline as solvents, the normal rearranged products were accompanied with 2- and 4-benzylphenols and 2- and 4-benzylquinolines. It was concluded that the pyrolysis of the secondary amines proceeds through their homolytic fission to benzyl and the corresponding toluidino free radicals. Homolysis of some primary products was also observed.
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