Issue 9, 2001

Thermal decomposition of tert-butyl ortho-(phenylsulfanyl)- and ortho-(phenylsulfonyl)phenyliminoxyperacetates: The reactivity of thio-substituted iminyl radicals

Abstract

Some ortho-(phenylsulfanyl)- and ortho-(phenylsulfonyl)-substituted phenyliminyl radicals have been generated by thermal decomposition of suitable tert-butyl iminoxyperacetates. The sulfanyl-substituted iminyls showed no tendency to give either 1,7- or 1,6-ring closure onto the S-phenyl ring. They gave instead 1,5-cyclisation onto the sulfur atom with release of a phenyl radical and formation of benzoisothiazoles. This seems to be the first example of SHi reaction of a nitrogen-centred radical at a sulfide moiety. On the other hand, the sulfonyl-substituted iminyl underwent 1,6-cyclisation to a small extent, furnishing a phenanthridine through an unprecedented 1,5-aryl radical migration from sulfur to nitrogen followed by loss of sulfur dioxide and ring closure of an aryl radical.

Graphical abstract: Thermal decomposition of tert-butyl ortho-(phenylsulfanyl)- and ortho-(phenylsulfonyl)phenyliminoxyperacetates: The reactivity of thio-substituted iminyl radicals

Article information

Article type
Paper
Submitted
06 Dec 2000
Accepted
27 Feb 2001
First published
12 Apr 2001

J. Chem. Soc., Perkin Trans. 1, 2001, 1072-1078

Thermal decomposition of tert-butyl ortho-(phenylsulfanyl)- and ortho-(phenylsulfonyl)phenyliminoxyperacetates: The reactivity of thio-substituted iminyl radicals

R. Leardini, H. McNab, M. Minozzi and D. Nanni, J. Chem. Soc., Perkin Trans. 1, 2001, 1072 DOI: 10.1039/B009843O

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