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The solvolyses of the p-nitrobenzenesulfonoxy derivatives of 2-methyl-2-octylamine,(7), 1-methylcyclohexylamine,(8), and 4, 7, 7-trimethyl-2-azabicycloheptane (10) and the m-(trifluoromethyl) benzenesulfonoxy derivative of dibenzylamine,(9) gave high yields of carbon-to-nitrogen rearrangementproducts. No parentamines were produced, even in the presence of heavy-atom solvents. The results, when compared to data from the literature, suggest that competing reaction pathways lead to rearranged or hydrogen abstraction products in the solvolysis of compounds with leaving groups attached to nitrogen.

Reaction intermediates involving positively charged, electrondeficient nitrogen atoms, nitrenium ions, have been a subject of considerable interest and some controversy. 2 Nitrenium ions are divalent nitrogen cations, which are isoelectronic with carbenes, and can exist in either a singlet, 1, or triplet, 2, spin state …