Initiation Chemistries in Hydrocarbon (Aut)Oxidation

For the (aut)oxidation of toluene to benzyl hydroperoxide, benzyl alcohol, benzaldehyde, and benzoic acid, the thermochemical profiles for various radical‐generating reactions have been compared. A key intermediate in all of these reactions is benzyl hydroperoxide, the heat of formation of which has been estimated by using results from CBS‐QB3, G4, and G3B3 calculations. Homolytic O?O bond cleavage in this hydroperoxide is strongly endothermic and thus unlikely to contribute significantly to initiation processes. In terms of reaction enthalpies the most favorable initiation process involves bimolecular reaction of benzyl hydroperoxide to yield hydroxy and benzyloxy radicals along with water and benzaldehyde. The reaction enthalpy and free energy of this process is significantly more favorable than those for the unimolecular dissociation of known radical initiators, such as dibenzoylperoxide or dibenzylhyponitrite.