Oxidation of dibenzothiophene by hydrogen peroxide or monopersulfate and metal-sulfophthalocyanine catalysts:: an easy access to biphenylsultone or 2-(2′-hydroxybiphenyl) sulfonate under mild conditions

A catalytic system consisting of metal-sulfophthalocyanines (MPcS) and monopersulfate or hydrogen peroxide as oxidants was effective in the dibenzothiophene oxidative desulfurization with various yields and selectivities. Oxidations were conducted at room temperature in acetonitrile-water mixed solvent. The dibenzothiophene oxidation involved the step by step formation of dibenzothiophene dioxide and biphenylsultone (dibenzo-1,2-oxathiine 2,2-dioxide), followed by hydrolysis to 2(2'-hydroxybiphenyl) sulfonate and finally catalytic desulfurization to 2-hydroxybiphenyl (2-phenylphenol) and sulfuric acid; all the intermediate compounds were identified. Moreover, catalytic over-oxidation of 2-hydroxybiphenyl, with ring fission and formation of various oxidation products, among them carbon dioxide, oxalic and benzoic acid, was also observed. Among the various MPcS catalysts examined (M=Fe, Co and Ru), the ruthenium derivative exhibited the best performances with persulfate and iron derivative with hydrogen peroxide; in both cases the slow step of the process consisted in the oxidation of dibenzothiophene dioxide to biphenylsultone.