Intramolecular free-radical substitution at the sulphur atom in sulphides

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Abstract
Aprotic diazotization of 2-aminophenyl 2-phenylthiophenyl (Ia), and of 2-aminophenyl 2-methylthiophenyl sulphide (Ib) in ethyl acetate gives rise to the corresponding deaminated products (III), dibenzothiophen derivatives (IV), and thianthren (II). Reactions carried out in anisole and nitrobenzene afforded a mixture of o-, m-, and p-methoxy- and -nitro-biphenyls; the isomer ratios were similar to those obtained in the phenylation of the same substrates with benzoyl peroxide. The same reaction carried out on 2-aminophenyl 2-phenylthiophenyl ether (VI) led to phenoxathiin and phenyl 2-phenylthiophenyl ether (VIII). A mechanism is proposed to explain the formation of the products; thianthren and phenoxathiin are assumed to form through an SHi reaction at the sulphur atom.

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