A kinetic investigation of the photochemical oxidation of certain non-conjugated olefins

Abstract

Photo-oxidation of cyclo hexene, 1-methyl cyclo hexene, dihydromyrcene and ethyl linoleate proceeds by a chain-reaction mechanism in which the initiation reaction is the photolytic generation of free radicals and the propagation and termination reactions are those recognized in analogous oxidations catalyzed differently. The magnitude of the primary quantum yield and quantitative correlation between the reaction rate and light absorption changes occurring during oxidation establish that the dominant initiation process is the photolysis of the olefin hydroperoxide. The special features which the reaction exhibits when the light absorption is either very weak or very strong are considered, and in the latter case it is shown that the basic kinetics are specifically modified.