Alj Beckwith

Cyclopolymerization. II. Electron Spin Resonance Studies of the Free-Radical Reactions of Some Diolefins

Abstract ESR spectra have been recorded for a number of radicals generated in a flow cell by interaction of diallylmalonic acid, diallyl ether, diallylamine, and related compounds with amino, hydroxyl, and phenyl radicals in aqueous solution. The results indicate that the radicals initially formed by homolytic addition at one of the double bonds in the diolefins rapidly undergo cyclization to afford product radicals containing five-membered rings.

Cyclopolymerization. III. Electron Spin Resonance Studies of Diallylamines with Redox Systems

Abstract The reaction of a series of diallylamines and related compounds with free radicals in aqueous acid solution has been studied in a flow system using ESR spectroscopy. The initiation was by radicals generated from titanium trichloride-hydrogen peroxide (hydroxyl radicals) and titanium trichloride-hydroxylamine (amino radicals) systems, respectively. The observed ESR spectra were assigned to five-membered ring radicals as the major radical species present in the system. However, the dimethallyl-amine series gave both five - and six-membered ring radicals.