Thermodynamics of competing oxidation reactions of allyl methyl disulfide by hydrogen peroxide: a first principle molecular computational study on the conformations of allyl methyl disulfide and its oxidized products

摘要

Allyl methyl disulfide, a peroxide scavenger, was studied together with three isomeric (two sulfoxides and one epoxide) forms of its mono-oxidized products. After a full conformational study of the reactant and three isomeric oxidized forms, the geometries were optimized at B3LYP/6-31G (d) level of theory. The epoxide form turned and to be more stable than either one of the two isomeric sulfoxides. Changes for Thermodynamic functions of oxidation reactions were calculated and from the G(reaction) values the equilibrium constant for the interconversions of the oxidized products were estimated. Bader-type AIM analyses were performed on the electron density, computed at the B3LYP/6-311++G (d,p) level of theory. In several of the sulfoxide conformations C-H center dot center dot center dot O=S< secondary interactions were observed. Copyright (C) 2008 John Wiley & Sons, Ltd.