New Chemistry of N-Nitroso- N,O-dialkylhydroxylamines and Related Compounds

Howard Maskill ,  Juan Crugeiras ,  Ana Rios ,  William McFarlane ,  Miguel A. Rios 

University of Newcastle, Newcastle NE17RU, United Kingdom

Abstract

A. The kinetics of nitrosation of dialkylhydroxylamines (RNHOR') have been investigated in aqueous acidic solution and shown to be compatible with a mechanism involving two channels. One involves direct reaction of the free hydroxylamine with nitrous acid, and the other involves reaction of the hydroxylamine with protonated nitrous acid.

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B. The interconversion of rotational isomers of N-nitrosodimethylhydroxylamine, MeN(NO)OMe, has been investigated by temperature-dependent NMR spectroscopy, and the enthalpy and entropy of activation have been determined. Comparison of the experimental results and values computed using high level MO theory indicates differing states of solvation of stable cis and trans isomers and the transition structure for their interconversion.

C. UV-Absorbance versus time data for the acid-catalysed decomposition of N-(2-adamantyl)hydroxydiazenium oxide indicate an unprecedented electrolyte-dependent autocatalytic mechanism via the less stable N-nitroso,N-adamantylhydroxylamine tautomer. The products of the reaction are 2-adamantanol and nitrous oxide (N2O).

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References:

[1] G. C. M. Bourke, G. Stedman, J. Chem. Soc. Perkin Trans. 2, 1992, 161.

[2] J. I. Bhat, W. Clegg, M. R. J. Elsegood, H. Maskill, I. D. Menneer, and P. C. Miatt, J. Chem. Soc. Perkin Trans. 2, 2000, 1435.

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Presentation: oral at 18th Conference on Physical Organic Chemistry, Symposium 1, by Howard Maskill
See On-line Journal of 18th Conference on Physical Organic Chemistry

Submitted: 2006-04-13 10:04
Revised:   2009-06-07 00:44
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