Liquid-phase oxidation of benzothiophene and dibenzothiophene by cumyl hydroperoxide in the presence of catalysts based on supported metal oxides

Abstract

The liquid-phase oxidation of benzothiophene and dibenzothiophene by cumyl hydroperoxide in the presence of supported metal oxide catalysts was carried out in octane in an N 2 atmosphere at 50–80°C. The cumyl hydroperoxide, benzothiophene, and dibenzothiophene conversions and the yield of sulfones were determined for catalysts of various natures. In the presence of MoO 3 /SiO 2 , the most efficient and most readily regenerable catalyst, the benzothiophene conversion was ∼60% and the dibenzothiophene conversion was as high as 100% upon almost complete consumption of cumyl hydroperoxide. The influence of unsaturated and aromatic compounds (oct-1-ene, toluene) on the catalytic effect was studied. The kinetics of substrate oxidation and cumyl hydroperoxide decomposition and an analysis of the cumyl hydroperoxide conversion products suggested a benzothiophene and dibenzothiophene oxidation mechanism including the formation of an intermediate complex of the hydroperoxide with the catalyst and the substrate and its transformation via heterolytic and homolytic routes.