Reactions of 2-Chlorocycloalkanone Oximes. I. Their Preparations and Conversion to 2-Alkoxy-, 2-Acyloxy- and 2-Alkylthiocycloalkanone Oximes

The preparation of 2-chlorocycloalkanone oximes has been investigated in detail. 2-Chlorocyclooctanone oxime is prepared in an excellent yield by the reaction of cyclooctene with nitrosyl chloride under the irradiation of light from a high-pressure mercury lamp. 2-Chlorocyclododecadienone oxime, 2-chlorocyclohexanone oxime and 3-chloronorcamphor oxime are prepared in good yields by the addition of nitrosyl chloride to cis, trans, trans-1, 5, 9-cyclododecatriene, cyclohexene and norbornene respectively in the presence of hydrochloric acid. Their displacement reactions with such nucleophilic reagents as sodium alkoxides, sodium ethanethiolate and sodium salts of carboxylicacids have been studied, and the syntheses of 2-alkoxy-, 2-ethylthio- and 2-acyloxy-cycloalkanone oximes have been successfully achieved.