AbstractThe reaction of peroxyhexanoyl nitrate, 1a, a homologue of the atmospheric pollutant “PAN”, 1b, with some twenty thioethers, is described. At 0‐25°C, common thioethers such as Et2S or PhSMe are rapidly converted into sulfoxides in high yields in a variety of solvents, ranging from pentane and chloroform to acetic acid, methanol and aqueous acetonitrile. Rates are essentially solvent‐independent, although the reaction is subject to marked steric hindrance. Relative rates for five p‐substituted thioanisoles in MeOH at 22°C, leading to a Hammett ρ‐value of ‐1.7, show that the sulfur atoms display nucleophilic character. Electron‐attracting groups on α‐carbon, such as in PhSCCl3 and in MeSCH2OC(O)Ph, inhibit the formation of sulfoxide. Addition of EtSH lowers the yield of sulfoxide, producing instead EtSSEt and EtSNO. Oxidation of Me2S by 1a with the NO2 group labelled by 18O does not give rise to 18O‐enriched DMSO. Comparison of (CH3)2S with (CD3)2S revealed an inverse kinetic H/D isotope effect.The products obtained from 1a vary with solvent. In the presence of water or EtSH, hexanoic acid is formed, while methanol gives rise to methyl hexanoate, and in pentane/hexanoic acid, hexanoic anhydride is produced. In aprotic solvents, significant amounts of CO2 are formed.These observations can best be rationalized on the basis of an intermediate sulfurane R1R2S(ONO2)(OCOR), (I), produced from thioether R1SR2 and 1a, in the first step. The fate of I under various conditions is discussed.Finally, the features of the oxidation of thioethers by peroxyacylnitrate are compared with those of acyl peroxides and peroxy esters. It is suggested that in each case formation of a sulfurane may well be the first step.