L. Barclay, J. Dust
Mar 1, 1982
Citations
0
Influential Citations
23
Citations
Journal
Canadian Journal of Chemistry
Abstract
Decomposition of N-nitroso-2,4,6-tri-tert-butylacetanilide (1) in benzene forms products 2,4,6-tri-tert-butylphenyl acetate (3), 3-(3,5-di-tert-butylphenyl)-2-acetoxy-2-methylpropane (4), and hydrocarbons 3-(3,5-di-tert-butylphenyl)- and 1-(3,5-di-tert-butylphenyl)-2-methylpropene (5 and 6) explained by a reactive aryl cation (2), the rearranged products (4, 5, 6) originating from a 1,5-hydride shift from an orthotert-butyl group in 2. In contrast, decomposition of 1 in triethylamine forms products 1,3,5-tri-tert-butylbenzene (10), 2,4,6-tri-tert-butylacetanilide (15), and 2-(3,5-di-tert-butylphenyl)-2-methylpropanal oxime (13), expected of a free radical pathway. Electron spin resonance evidence is given for intermediates formed by rearrangement of the 2,4,6-tri-tert-butylphenyl radical and spin trapped by the nitroso group of 1. CIDNP and esr studies on the dediazoniation of N-nitrosoacetanilide and aniline in the presence of tertiary amines support the proposed electron transfer mechanism. The results ...