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N-nitroso-N,O-dialkylhydroxylamines: Preparation, structure, and mechanism of the hydronium ion catalysed solvolytic nitrous oxide extrusion reaction

Lookup NU author(s): Emeritus Professor Bill Clegg, Dr Mark Elsegood, Dr Peter Miatt


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Eleven N-nitroso-N,O-dialkylhydroxylamines, RN(NO)OR′, have been prepared and the mechanisms of their hydronium ion catalysed solvolyses in aqueous solution which liberate nitrous oxide have been investigated. All reactions are first-order in substrate and first-order in hydronium ion, and the second-order rate constants at 25°C vary over a range of less than 140 in spite of considerable variation in substrate structure (R ranges from methyl to 4-methoxybenzyl to 2-adamantyl, for example) and changes in solvent composition (water with up to 50% methanol or 66% acetonitrile). Enthalpies and entropies of activation are qualitatively similar throughout the range (ΔH‡= 72-93 kJ mol-1 and ΔS‡ = -19 to -57 J K-1 mol-1) which, with the product analyses, are accommodated by a mechanism involving pre-equilibrium protonation of the substrates followed by rate-limiting dissociation to give RN2O+ and HOR′. The oxodiazonium ion intermediate, RN2O+, then dissociates further to give the carbenium ion intermediate, R+, or suffers direct nucleophilic displacement of N2O by solvent (the external nucleophile) or by R′OH (the internal nucleophile liberated in the initial fragmentation). The carbenium ion, R+ (if formed), suffers nucleophilic capture either by solvent or by R′OH. When acetonitrile is the co-solvent (rather than methanol) for the N-(2-adamantyl) substrate 3g, the product of the Ritter reaction, 2-acetamidoadamantane, is detected. These nitrous oxide liberating reactions are compared with the nitric oxide liberating reactions of related N-nitrosohydroxylamines, and the origin of the difference between them is identified. The N(1)-nitroso group in the N,O-dibenzyl compound 3c is shown by X-ray crystallography to be essentially coplanar with the C and O atoms also bonded to N(1).

Publication metadata

Author(s): Elsegood MRJ; Clegg W; Miatt PC; Bhat JI; Maskill H; Menneer ID

Publication type: Article

Publication status: Published

Journal: Journal of the Chemical Society. Perkin Transactions 2

Year: 2000

Issue: 7

Pages: 1435-1446

ISSN (print): 0300-9580

ISSN (electronic): 1364-5471

Publisher: Royal Society of Chemistry


DOI: 10.1039/b001688h


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