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Amine-N-oxide rearrangements

1970; Elsevier BV; Volume: 26; Issue: 18 Linguagem: Inglês

10.1016/s0040-4020(01)93077-7

1464-5416

Neal Castagnoli, J. Cymerman Craig, Anita Melikian, S.K. Roy,

Chemical Reactions and Isotopes

The thermolysis of a series of structurally similar amine-N-oxides has been examined individually and as mixtures. Product analysis shows that in addition to the expected N-alkoxylamines, smaller amounts of t-amines, aldehydes, and bibenzyls are formed. Thermolysis of mixtures produces intermolecular rearrangement products thus challenging the previously favored intramolecular mechanism as the exclusive process for the Meisenheimer rearrangement. The data are consistent with a mechanism involving homolytic fission to intermediates which recombine to produce the N-alkoxylamines.