Photoreaction of nitroso compounds in solution. XI. Secondary reactions in the photoaddition of N-nitrosopiperidine to olefins

Abstract

Irradiation of N-nitrosopiperidine and 3,3-dimethyl-1-butene in a Pyrex apparatus gave 3,3-dimethyl-1-piperidino-2-(N-nitrosohydroxylamino)butane as the major product, in contrast to similar additions to 1-hexene and other olefins. Depending on the conditions, minor amounts of 3,3-dimethyl-1-piperidino-2-(N-hydroxylformamido)butane and 3,3-dimethyl-1-piperidino-2-butanone oxime were also isolated. It was proposed that the butane derivatives were formed by the reactions of the C-nitroso monomer with HNO and formaldehyde respectively which were photolytically generated from N-nitrosopiperidine and methanol. In agreement with this proposal, irradiation of a mixture of trans-dimer of 1-piperidino-2-nitrosohexane and N-nitrosopiperidine gave 1-piperidino-2-(N-nitrosohydroxylamino)hexane. By adjusting the irradiation conditions, this nitrosohydroxylamine could be obtained as the major product from addition of the nitrosamine to 1-hexene.