Photolysis of nitroso compounds-III. 2-Nitro-2-nitrosopropane

The photodecomposition of 2-nitro-2-nitrosopropane (2-propylpseudonitrole) with light of ? > 540 nm was studied. The product distribution changes drastically with the nature of the solvent but can be explained readily by homolytic cleavage of the CNO bond. No evidence of photoreduction by an excited state of the nitrosocompound was obtained. In aprotic solvents the major products were acetone, 2,2-dinitropropane, 2-nitropropene, nitrogen dioxide, nitric oxide and nitrogen. In methanol methyl nitrite, acetoxime, acetone dimethylketal and acetone together with dinitrogen monoxide and water were the main products. This pronounced solvent influence is shown to be caused by the solvolysis (in methanol) or secondary thermal decomposition (in aprotic solvents) of labile intermediates. The 2-nitropropyl radical formed in the primary dissociative step does not take part in any hydrogen abstraction reactions under the experimental conditions employed. © 1973.