Cyclopolymerization. XII. Electron spin resonance studies of the free radical reactions of β-substituted diallylamines

Abstract

E.s.r. spectra, and the effects of different β-substituents on the structures and relative proportions of isomeric pyrrolidin-3-ylmethyl and piperidin-3-yl radicals formed during cyclization of N,N-diallylmethylamines, are described. The hypothetical intermediate 4-azahept-6-en-2-yl radicals undergo preferential cyclization to pyrrolidin-3-ylmethyl radicals, but the sensitivity of this process to steric and conjugative effects is shown by the tendency of intermediate radicals derived from suitable substituted diallylamines to undergo alternative cyclization to piperidin-3-yl radicals.