N-nitrosoamide-mediated N → O nitroso transfer to alcohols with subsequent denitroxylation

(Chemical Equation Presented) Decomposition of certain N-benzyl-N- nitrosoamides is often accompanied by small amounts of benzaldehyde whose formation was postulated to arise from in situ formation and oxidation of benzyl alcohol. Incubation of excess benzyl alcohol with thermostable N-benzyl-N-nitrosoamides at ambient temperatures in inert solvents generates benzyl nitrite, N-benzyl amides, and benzaldehyde as the major products. Benzyl nitrite formation appears to be linked to N → O nitroso transfer between the N-benzyl-N-nitrosoamides and benzyl alcohol, which is subject to the previously observed electronic and steric features of the acyl substituent although the former appears to play a much larger role than the latter. Benzaldehyde formation evidently arises from dehydronitrosation (denitroxylation) of the nitrite via O-N bond homolysis and H-abstraction from the resultant benzyloxy radical. Although trans-nitrosation occurs with methanol, 1°, 2°, and 3° alcohols, the reaction is evidently subject to steric effects at both the α and β carbons of the alcohol. Additionally, carbonyl formation only occurs with 2° alcohols and those that can derive resonance-stabilized carbonyls.