Model copolymerization reactions: Evidence against stereochemical effects of donor-acceptor complexation in reactions of simple alkyl radicals with n-phenylmaleimide and donor olefins

Abstract

Reductive demercuration of alkylmercuric bromides with NaBD_4 was used to generate the 1-butyl and t-butyl radicals in mixtures of N-phenylmaleimide (NPM) and either of the donor olefins 2-chloroethyl vinyl ether (CEVE) or tetrathiafulvalene (TTF). In each case, the major products of the reaction were derived from simple addition of the radical to NPM followed by transfer of a deuterium atom to the initial adduct. There were no differences in the stereochemistries of the products formed from reaction mixtures of widely varying monomer compositions. These results show that transfer of the deuterium atom to the radical center is unaffected by electron donor-acceptor (EDA) complexation and argue against important stereochemical consequences of EDA complexation in radical copolymerization.

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