Nucleophilic character of alkyl radicals—VIII : Kinetics and mechanism of induced decomposition of decanoyl peroxide in the homolytic alkylation of protonated quinoline

Abstract

The thermal decomposition of decanoyl peroxide in benzene, heptane, quinoline, acetic add and quinoline in acetic acid was studied. Kinetics and reaction products in the first four solvents follow the usual pattern of the acyl peroxides decomposition. However, in the presence of protonated quinoline a remarkable example of induced decomposition was found. First-order kinetics in peroxide indicates that a cross-termination is operative in a radical chain. The composition of the reaction products is also highly simplified in comparison with that obtained in the other solvents: only 2- and 4-nonylquinolines, decanoic acid and traces of octadecane are formed. Kinetics and reaction products are discussed in terms of a free-radical chain mechanism, in which the nucleophilic character of the nonyl radical plays an important role.