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The capacity of an α-nitroalkyl radical for hydrogen abstraction

1975; Elsevier BV; Volume: 31; Issue: 8 Linguagem: Inglês

10.1016/0040-4020(75)80120-7

1464-5416

T. A. B. M. Bolsman, J. W. Verhoeven, Th. J. de Boer,

Chemical Reaction Mechanisms

Photochemical decomposition of 2-iodo-2-nitroadamantane in several hydrogen donating solvents, gives rise to formation of α-nitroalkyl radicals. Such ambident radicals can abstract hydrogen from the solvent via oxygen, resulting in a nitronic acid which decomposes exlusively into adamantanone. Alternately the abstraction can take place via carbon to give 2-nitroadamantane. The product distribution is strongly influenced by electron-withdrawing substituents in the hydrogen donor. The oxidation products derived from the solvent have been detected. All the experiments point towards a minor stabilisation of a carbon radical by a nitro group. INDO-calculations on the nitromethyl radical are in good agreement with this lack of stabilization.