Molecular Rearrangements. Part IV. Aryl (Alkyl) Amines (1), Thermal Rearrangement of <i>N</i>-Benzyl-<i>N</i>-Methylaniline

Abstract

Heating N-benzyl-N-methylaniline under reflux or heating at ∼315° in sealed tubes, in the absence of any promotor for 100 h, resulted in its rearrangement, producing methylamine, diphenylmethane, and dibenzyl together with o-toluidine and 4-methylacridine. Heating N-methylaniline in a sealed tube under the same conditions, in absence of any promotor, resulted in its rearrangement, producing methylamine and o-toluidine together with unidentified neutral products.When pyrolysis of the tertiary amine was carried out with quinoline as a solvent, the normal products of rearrangement were obtained together with 2-and 4-benzylquinolines and 2,2′-biquinolyl.The reaction mechanism is discussed on the basis of the products separated, from which it is concluded that the tertiary amine undergoes homolytic fission to benzyl and N-methylphenylamino free radicals, followed by a series of homolytic fissions of initially separated intermediate products, during the rearrangement process. Throughout the whole mechanism, the C—N bonds are the only ones to suffer homolytic fission.