Reaction of Nitrosyl Chloride Gas with Unsaturated Steroids

Article abstract of DOI:10.1246/bcsj.60.3411

Reaction of nitrosyl chloride gas at 0 deg C with 3,5-cholestadiene (1) provided 3,6β-dinitro-5-chloro-5α-cholest-3-ene (4) and with 3α,5-cyclo-5α-cholestan-6-one (2) afforded 3β-chloro-5-nitro-5α-cholestan-6-one (7) and 3β-chloro-6-nitrato-5-cholestene (8).Similar reaction with 6-hydroxylimino 3α,5-cyclo-5α-cholestane (3) gave 3β,6-dichloro-6-cholestene (10), 3β-chloro-6-nitratoimino-5α-cholestane (11) and 3β,5-dichloro-6-nitroimino-5β-cholestane (12).Compound 12 upon hydrolysis furnished 3β,5-dichloro-5β-cholestan-6-one (14).The structures of these compounds were established on the basis of their spectral properties, and some pertinent chemical transformations.Mechanisms for the formation of some unusual products are discussed.