Photolysis of nitroso-compounds. Part IV. 1-Chloro-1-nitrosocyclohexane and other geminal chloro-nitroso-compounds

摘要: Detailed studies of the photolysis 1-chloro-1-nitrosocyclohexane are presented. Photolysis in methanol solutions gave hydrochloric acid, methyl nitrite, 1,1-dimethoxycyclohexane, cyclohexanone, and cyclohexanone oxime. 1-Methoxycyclohexene 6-hydroxyimino-1-methoxycyclohexene were minor products. aprotic solvents afforded 1-chlorocyclohexene, 1,1-dichlorocyclohexane with small amounts α-chlorocyclohexanone 1-chloro-1-nitrocyclohexane at low concentrations whereas high substantial oxime found. Evidence based on variation product distribution solvent, concentration, added radical scavengers is presented, which shows that primary photochemical step consists C–NO bond cleavage all solvents. α-Chloronitrones postulated as intermediates. The importance solvolysis other secondary ionic reactions emphasised. Other geminal chloronitrosoadamantane, 3-chloro-3-nitrosopentane, 2-chloro-2-nitrosobutane alcohols briefly re-examined light proposed mechanism. In none these cases have we found any evidence for a carbonyl-like photoreduction.