THE ELECTRON-INDUCED FRAGMENTATION OF LARGE RING CYCLOALKYLAMINES - INTRAMOLECULAR REACTIONS BETWEEN RADICAL AND IMMONIUM WITHIN DISTONIC IONS

The unimolecular reactivity of molecular radical cations of secondary and tertiary cycloalkylamines in the gas phase is explained by the reactivity of the radical. Two competing reactions are crucial: the displacement of the radical along the hydrocarbon chains by hydrogen transfers leading to a series of distonic ions, and the reaction of the radical with the immonium group, in each distonic ion, leading to cyclic structures. The resulting rearranged parent ions fragment subsequently by losing homologous alkyl radicals.