Mechanisms of photochemical reactions of para-benzoquinones with thiols

Abstract

The mechanisms of quinone reduction by thiols containing α-hydrogen atoms were established using chemically induced dynamic nuclear polarization effects. It was found that substituents in the quinone nucleus change the nature of the primary radical pair. In the photolysis of 2,6-dimethyl-1,4-benzoquinone (1), the radical pair consists of semiquinone and thioalkyl radicals, whereas in the case of 2,6-diphenyl-1,4-benzoquinone (2), the radical pair is composed of semiquinone and thiyl radicals. Quinone 2 is readily photolyzed with any thiol to give dibenzofuran derivative as the final products.