The photolysis of C-nitroso-compounds. Part 8. The solution photolysis of some tertiary C-nitroso-compounds

The photolysis of the nitrosoalkanes 2-methyl-2-nitrosopropane (I), 2-nitroso-2-phenylpropane (II), 2-benzyl-2-nitrosopropane (III), and 1-nitrosoadamantane (IV) with visible light (? > 540 nm) yielded trialkylhydroxylamines and, with the exception of (IV), alkenes as main products. In methanol the alcohols, alkyl nitrites, and methyl nitrite were obtained additionally. These products are rationalised on the basis of a homolytic dissociation into a free radical and nitric oxide in the primary step. The reaction of nitric oxide with the substrate rather than a direct photoelimination of HNO is identified as the major source of alkenes.