826-07-3Relevant articles and documents
Mechanism of sulfone formation in the reaction of sulfides and singlet oxygen: Intermediacy of S-hydroperoxysulfonium ylide
Ishiguro, Katsuya,Hayashi, Masaki,Sawaki, Yasuhiko
, p. 7265 - 7271 (1996)
H-D exchange was observed in the methyl group during the formation of sulfones in the reaction of dimethyl sulfide-d6 or thioanisole-α,α,α-d3 with singlet oxygen in aprotic solvents. No exchange was observed in the sulfoxides obtained. The proton in the sulfones was shown to come from adventitious water, since the oxidation of C6H5SCH3 in the presence of D2O lead to the formation of sulfones with monodeuteriation. The 16O2-18O2 tracer study demonstrated no oxygen scrambling in the sulfones. All the results indicate that the sulfones are formed intramolecularly via an intermediate possessing one activated proton exchangeable with trace water, a suggested structure for which is S-hydroperoxysulfonium ylides (RS+(OOH)CH2-). Kinetic isotope effects (k(H)/k(D) = 2-4) observed for methyl protons in the sulfone formation suggest that the rate-determining step is the intramolecular proton abstraction in the persulfoxides (RS+(OO-)CH3) generating S-hydroperoxysulfonium ylides. The conversion of the ylide intermediates to sulfones is shown to be facile on the basis of PM3 theoretical calculations.
Reaction of singlet oxygen with thioanisole in ionic liquids: A solvent induced mechanistic dichotomy
Baciocchi, Enrico,Chiappe, Cinzia,Del Giacco, Tiziana,Fasciani, Chiara,Lanzalunga, Osvaldo,Lapi, Andrea,Melai, Bernardo
supporting information; experimental part, p. 1413 - 1416 (2009/09/24)
A study of the reaction of thioanisole with singlet oxygen in pyrrolidinium-and imidazolium-based ionic liquids has been carried out. In these solvents, thioanisole shows a strongly enhanced reactivity with respect to molecular aprotic solvents, probably