On the regioselectivity of free radical processes ; reactions of benzoyloxy, phenyl and t-butoxy radicals with some α,β-unsaturated esters

Abstract

The reactions of three electrophilic radicals, benzoyloxy, phenyl, and t-butoxy, have been examined with a series of α, β unsaturated esters; methyl acrylate, methyl methacrylate, and methyl crotonate. For the three monomers the ratio of hydrogen abstraction to double bond addition was found to increase and the ratio of head against tail addition to decrease in the series: benzoyloxy; phenyl; t-butoxy. Relative rates for these reactions have been determined and the factors influencing the mode of reaction are discussed.