Generation and reactions of aryl and alkyl thionitroso compounds

Transient thionitrosoarenes (102) with para substituents have been generated from N-(arylaminothio)-phthalimide derivatives (101) and intercepted with chloroprene and piperylene to give regioisomeric Diels- Alder adducts. Reaction of thionitrosoarenes (102) with 1-methylcyclohexene, a-pinene and β-pinene gave sulphenamides. Sulphenamides (110) and(123) have been reacted with 2,6-difluorobenzoylisocyanate. Heteroaryl thionitroso compounds have been prepared. Thionitrosoarenes with an ortho substituent have been generated via two different routes and trapped with 2,3-dimethyl-l,3-butadiene to give mixtures of Diels-Alder and ene adducts; the ene adduct was the major isomer for each system. Thionitrosoarene (159b) was generated from 3- aminobenzisothiazole (157b) using lead tetraacetate and was intercepted with 2,3-dimethyl-l,3-butadiene to give Diels-Alder (160) and ene (161) adducts. Thionitrosoalkanes have been generated using two different routes and trapped with 2,3-dimethyl-l,3-butadiene to give Diels-Alder and ene adducts.