71426-19-2Relevant academic research and scientific papers
Photosensitized oxidation of aryl benzyl sulfoxides. Evidence for nucleophilic assistance to the c-s bond cleavage of aryl benzyl sulfoxide radical cations
Del Giacco, Tiziana,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Mencarelli, Paolo
, p. 2310 - 2318 (2015)
The radical cations of a series of aryl benzyl sulfoxides (4-X-C6H4CH2SOC6H4Y+?) have been generated by photochemical oxidation of the parent sulfoxides sensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ+ClO4-). Steady-state photolysis experiments showed the prevailing formation of benzylic products deriving from the C-S fragmentation in the radical cations, together with sulfur-containing products. Formation of sulfoxide radical cations was unequivocally established by laser flash photolysis experiments showing the absorption bands of 3-CN-NMQ? (λmax = 390 nm) and of the radical cations (λmax = 500-620 nm). The decay rate constants of radical cations, determined by LFP experiments, decrease by increasing the electron-donating power of the arylsulfinyl Y substituent and to a smaller extent by increasing the electron-withdrawing power of the benzylic X substituent. A solvent nucleophilic assistance to the C-S bond cleavage has been suggested, supported by the comparison of substituent effects on the same process occurring in aryl tert-butyl sulfoxide radical cations. DFT calculations, performed to determine the bond dissociation free energy in the radical cations, the transition state energies associated with the unimolecular C-S bond cleavage, and the charge and spin delocalized on their structures, were also useful to endorse the nucleophilic assistance to the C-S scission.
THE THIO-ARBUZOV-REACTION. PART 7. UNSYMMETRIC SULFOXIDES PhS(O)CH2R FROM METHYL BENZENESULFENATE AND BROMOALKANES RCH2Br
Kersten, Mathias,Wenschuh, Eberhard
, p. 81 - 84 (2007/10/02)
Alkylation reactions of methyl benzenesulfenate with bromoalkanes were studied and found to follow the Thio-ARBUZOV pathway.The reaction concept was extended to the conversion of sulfenates into unsymmetric sulfoxides.Thus four new unsymmetric sulfoxides could be obtained and the synthesis of others already mentioned in the literature was improved. Key words: Thio-ARBUZOV-Reaction; methyl benzenesulfenate; bromoalkanes; unsymmetric sulfoxides; nitromethane; 19F-NMR data.
