LIQUID-PHASE OXIDATION OF HYDROCARBONS WITH MOLECULAR-OXYGEN .1. EFFECTS OF METAL-IONS AND THEIR LIGANDS ON PRODUCT DISTRIBUTION IN OXIDATION OF TETRALIN IN ACETIC-ACID

Metal-ion catalyzed oxidation of tetralin and metal-ion catalyzed decomposition of alpha -tetralin hydroperoxide (THP) were carried out in acetic acid in both the presence and absence of an additive. It was found that the rate-determining step in the oxidation of tetralin is the decomposition of THP. The results also suggest that the decomposition of THP with cobalt catalysts proceeds by the inner-sphere mechanism. In the oxidation of tetralin catalyzed by first-transition-metal ions, excepting vanadium, cobalt showed the highest activity and the lowest selectivity of hydroperoxide, and chromium showed the highest ratio of alpha -tetralone to alpha -tetralol (On/Ol). The order of the activities of metal acetates in producing oxidation is in agreement with that of the activities of metal acetates in producing decomposition. Such agreement is also found for Co(acac)//3, Cr(acac)//3, Mn(acac)//2, and Fe(acac)//3 catalysts.