PHOTOSENSITIZED ANAEROBIC OXIDATION OF DIBUTYL SULFIDE

Upon photoexcitation, acetone can function as an oxidant for dibutyl sulfide by a low quantum yield route (ϕ = ~0.016). A complex mixture of photoproducts results. Solvent effects, kinetics, product distributions, and quenching studies indicate that a radical pathway is important. Unlike the analogous oxidation of methionine, both sulfoxide and sulfone are produced along with smaller quantities of sulfur-containing products produced from radical fragments. In addition to acting as an oxygen source, acetone undergoes normal solution-phase photoreactions and significant polymerization. A mechanism for the oxygen-transfer process is suggested, and experiments which examine the generality of this photoprocess are described. © 1979, American Chemical Society. All rights reserved.