Comparative analysis of diacylated peroxide methanol solution decomposition under temperature and microwave radiation

Abstract

Thermolysis of benzoyl and acetylbenzoyl peroxides in methanol-d4 under temperature and microwave radiation treatment was studied. It was shown that chemical induced dynamic nuclei polarization can be observed even when reaction is carried out in spectrometers with high magnetic fields. In this case spin correlation in geminate radical pairs with labile aceloxy radicals persists. Equal quantity of products is obtained independent of the way of peroxide decomposition initiation. Homolysis proceeds according to chain mechanism. Contribution of induced decomposition decreases while reaction proceeding. Molecules of dissolved oxygen terminate the chain effectively, decreasing the rate of the reaction of peroxide decomposition. In the case of acetylbenzoyl yield of products depends of initiation mechanism: under microwave radiation treatment molecules of solvent are more active, but dissolved oxygen is less active than under thermolysis condition.