70501-88-1Relevant articles and documents
Base-Induced Fragmentation of β-Hydroxy Nitrosamines
Loeppky, R. N.,McKinley, W. A.,Hazlitt, L. G.,Outram, J. R.
, p. 4833 - 4841 (1982)
β-Hydroxy nitrosamines have been found to undergo a base-induced fragmentation reaction.The reaction cleaves the Cα-Cβ bond of the substrate to produce an aldehyde or ketone and a smaller alkylnitrosamine.Rate contants for the fragmentation induced by potassium tert-butoxide in THF or tert-butyl alcohol have been measured for nine substrates at temperatures between 35 and 70 deg C.The rate constants are a function of base concentration and range between 0.15x10-6 and 308x10-6 s-1.Rate constants have been determined for (2-hydroxyethyl)methylnitrosamine,N-nitrosodiethanolamine, (2-hydroxy-2-methylpropyl)methylnitrosamine, (2-hydroxy-2-phenylethyl)methylnitrosamine, N-nitrosoephedrine, (2-hydroxy-2,2-diphenylethyl)methylnitrosamine, and (2-hydroxy-2-phenylpropyl)methylnitrosamine.The nitrosamino alcohol fragmentation rates are in the order tertiary > secondary > primary, and the rate appears to be a function of product stability and steric strain in the substrate.A mechanism which accounts for these observations is proposed.
