US EPA

1043069 

Journal Article 

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

Darbeau, RW; Alvarez, N; Aymond, RN 

2005 

Yes 

Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 

70 

8 

3225-3230 

English 

15822985 

10.1021/jo050011g 

WOS:000228367100039 

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 degree, 2 degree, and 3 degree alcohols, the reaction is evidently subject to steric effects at both the alpha and beta carbons of the alcohol. Additionally, carbonyl formation only occurs with 2 degrees alcohols and those that can derive resonance-stabilized carbonyls.