Photolysis of Dibenzoyl Peroxide under Direct and Singlet Sensitized Irradiations. Mechanism for the Formation of the Geminate Product

Abstract

Attempts have been made to elucidate the mechanism for the efficient production of phenyl benzoate, the geminate product, from direct and singlet sensitized irradiations of dibenzoyl peroxide in solution. It is concluded that these irradiations produce a reactive state of the peroxide which can undergo two-bond cleavage of the O–O and C(α)–C(carbonyl) bonds to give a phenyl–benzoyloxy radical pair in a solvent cage, followed by the recombination of the component radicals to give the geminate product or by their diffusion out of the solvent cage to give diffusion products.