Toggle Main Menu Toggle Search

Open Access padlockePrints

The Newcastle University research output collection, currently available on ePrints, will shortly be moving to a new open repository platform, Figshare. To prepare for the data migration we have paused adding new content to ePrints, and will resume once the new repository is launched. During this time you will continue to have access to ePrints (but no new content will appear). We will share updates here when available.

N-tritylhydroxylamines: Preparations, structures, base strengths, and reactions with nitrous acid and perchloric acid

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

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.

Abstract

N-Trityl, N-(4-methoxytrityl), N-(4,4′-dimethoxytrityl), and N-(4,4′,4″-trimethoxytrityl) derivatives of hydroxylamine, O-methylhydroxylamine, and O-benzylhydroxylamine have been prepared and characterised. Additionally, N,O-ditrityl- and N,O-bis(4,4′-dimethoxytrityl)-hydroxylamines have been made, and the X-ray crystal structure of the former has been determined. The pKa value of O-benzylhydroxylammonium in water (6.2) and of its N-trityl analogue in aqueous acetonitrile (7.5) have been measured. The N-tritylhydroxylamines all decompose under aqueous acidic conditions to give the corresponding trityl alcohols, and rate constants for uncatalysed and hydronium ion catalysed reactions of N-(4,4′-dimethoxytrityl)-O-methylhydroxylamine have been measured by stopped flow kinetics at 25°C. This compound compares in reactivity with N-alkyl-N-(4,4′-dimethoxytrityl)amines rather than with 4,4′-dimethoxytritylamine. Attempted nitrosation of N-tritylhydroxylamine and its O-alkyl derivatives gave trityl alcohol, the intermediate N-nitroso compound being detectable but too unstable to isolate. From N-trityl-O-benzylhydroxylamine, attempted nitrosation led to the formation of triphenylmethane in addition to trityl alcohol, benzyl alcohol, and trityl benzyl ether. The mildly acidic conditions used for attempted nitrosation of methoxy-substituted N-tritylhydroxylamines led to deamination before addition of the nitrosating agent.

Publication metadata

Author(s): Canle LM, Clegg W, Demirtas I, Elsegood MRJ, Haider J, Maskill H, Miatt PC

Publication type: Article

Publication status: Published

Journal: Journal of the Chemical Society, Perkin Transactions 2

Year: 2001

Issue: 9

Pages: 1742-1747

ISSN (print): 1472-779X

ISSN (electronic): 1364-5471

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b103569j

DOI: 10.1039/b103569j

Altmetrics

Altmetrics provided by Altmetric

Share