Generation of thionitrosoarenes (ArNS) from N-(arylaminothio)phthalimides and in situ trapping with alkenes and conjugated dienes

摘要: A series of N-(arylaminothio)phthalimide derivatives (7a–h) has been prepared by reaction phthalimidesulphenyl chloride with the trimethylsilyl derivative appropriate arylamine. On treatment triethylamine at room temperature, compounds (7) fragment to yield transient thionitroso species (8). Derivatives (8a–h) have trapped in good as their Diels–Alder adducts [e.g. N-aryl-1,2-thiazine (9) and (10)] following conjugated dienes: butadiene, 2,3-dimethylbutadiene, 1,4-diphenylbutadiene, (E,E)- (E,Z)-hexa-2,4-diene, 1,1′-bicyclopentenyl (25) 1,1′-bicyclohexenyl (26). The stereochemistry diene is retained (19)–(24). Thionitrosoarene (8) also afford sulphenamide derivatives, e.g.(11) (12)–(16), ene addition dimethylbutadiene, isobutene, α-methylstyrene. N-Aryliminosulphur dichlorides (34) react 2,3-dimethylbutadiene 1,2-thiazine products, probably way thionitrosoarene intermediates.