Search

The reaction of sulfoxides with peroxy acids in various organic media was studied. The reaction mechanism involves the rapid formation of a sulfoxide-–peroxy acid intermediate which decomposes in the second stage to form carboxylic acid and the corresponding sulfone. The second stage is the rate-limiting step. The reaction medium significantly affects the rate of oxidation. The calculated activation parameters of the oxidation process indicate a compensation effect in the investigated reaction. Correlations between the main physicochemical parameters of solvents and the effective rate constants (k) of dimethyl sulfoxide oxidation with peroxy acids were found. Depending on the reaction conditions, the main factors affecting the k values are specific and nonspecific solvation of the reactants and structural factors. [ABSTRACT FROM AUTHOR]

Thermal decomposition of peroxydecanoic acid has been investigated in various organic solvents. The reaction medium significantly affects the rate of peroxydecanoic acid thermal decomposition. It has been shown that primary homolytic decomposition of peroxy group is followed by induced radical chain decomposition reactions. The solvent nature influences both primary homolytic decomposition and secondary induced reactions. The correlation equations relating kinetic parameters of peroxydecanoic acid thermolysis and basic solvent properties have been derived. [ABSTRACT FROM AUTHOR]