Thermodynamics of competing oxidation reactions of allyl-methyl disulfide by hydrogen peroxide. a first principle molecular computacional study

MATíAS F. ANDRADA; JUAN C. GARRO MARTíNEZ; GRACIELA N.ZAMARBIDE; FRANCISCO TOMáS VERT; BELA VISKOLCZ; MARIO R. ESTRADA; IMRE G.CSIZMADIA

Los Cocos, Córdoba, Argentina

Conferencia; 9º Conferencia Latinoamericana de Físico Química Orgánica; 2007

Abstract 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 ÄGreaction 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···O=S< secondary interactions were observed.