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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

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

Fawaz Aldabbagh, W. Ken Busfield and Ian D. Jenkins

Australian Journal of Chemistry 54(5) 313 - 318
Published: 30 November 2001

Abstract

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–S compounds—a sulfoxamide and a sufonamide—not the expected N–O–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.

https://doi.org/10.1071/CH01100

© CSIRO 2001

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