
%0 Journal Article
%A Aldabbagh, Fawaz 
%A Busfield, W. Ken 
%A Jenkins, Ian D. 
%T The Reactivity of Sulfur-Centred Radicals towards TMIO (1,1,3,3-Tetramethyl-2,3-dihydroisoindol-2-yloxyl). A New Type of Radical Fragmentation Reaction
%J Australian Journal of Chemistry
%D 2001/11/29
%V 54
%N 5
%P 313-318
%K 
%R https://doi.org/10.1071/CH01100
%U https://www.publish.csiro.au/paper/CH01100 
%X The thiyl radicals derived from 2-mercaptoethanol and thiophenol were found to undergo a complex series of reactions with 1,1,3,3-tetramethyl-2,3-dihydroisoindol-2-yloxyl (TMIO). Thus, treatment of 2-mercaptoethanol with di-t-butyl peroxyoxalate (DTBPO) in the presence of TMIO produced two N&#8211;S compounds&#8212;a sulfoxamide and a sufonamide&#8212;not the expected N&#8211;O&#8211;S adduct. The reaction between thiophenol and TMIO, which proceeded at a reasonable rate in the absence of DTBPO, produced 1,1,3,3-tetramethyl-2,3-dihydroisoindolin and its corresponding phenylsulfoxamide, diphenyl disulfide, phenylsulfinic acid, and 1,1,3,3-tetramethyl-2,3-dihydroisoindol-2-ylphenylsulfonate (the adduct of TMIO and the phenylsulfonyl radical). The mechanism of formation of these products, and the use of TMIO for trapping S-centred radicals, are discussed. A new radical fragmentation process, which appears to be general for aminoxyl adducts of electron-rich systems, is described. 
