N-phenylsulphimide formation and rearrangement in the thermal reaction of phenylnitrene with sulphides

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Thermal reaction of phenyl azide (1) with thioanisole (2a), dimethyl sulphide (2b), and tetrahydrothiophen (2c) leads to the formation of 2-substituted anilines (3a–c) by Sommelet–Hauser rearrangement of the intermediate N-phenylsulphimides arising from phenylnitrene attack at the sulphur atom of (2a–c). Reaction with ethyl phenyl sulphide (2d) gives benzenesulphenanilide (8) and ethylene by cycloelimination of the resulting N-phenylsulphimide. Reaction with acyclic benzylic sulphides (2e–g) apparently leads only to the insertion products of phenylnitrene into the benzylic C–H bond, presumably through Stevens rearrangement of the intermediate sulphimides, whereas Sommelet–Hauser rearrangement appears to compete favourably with Stevens rearrangement in the sulphimide resulting from reaction of phenylnitrene with the cyclic benzylic sulphide (2h).