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Reactivity and the mechanism of reactions of β-sultams with Nucleophiles

Wood, J. Matthew, Hinchliffe, Paul S., Laws, Andrew P. and Page, Michael I. (2002) Reactivity and the mechanism of reactions of β-sultams with Nucleophiles. Journal of the Chemical Society Perkins Transactions 2. pp. 938-946. ISSN 1364-5471

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Abstract

Ethane-1,2-sultam has a pKa of 12.12 ± 0.06 at 30 C and its rate of alkaline hydrolysis shows a pH-dependence
reflecting this so that the observed pseudo first-order rate constant at pHs above the pKa are pH independent. There
is no evidence of neighbouring group participation in the hydrolysis of either N-α-carboxybenzylethane-1,2-sultam
or N-(hydroxyaminocarbonylmethyl)-2-benzylethane-1,2-sultam. Oxyanions, but not amines or thiols, react with
N-benzoylethane-1,2-sultam in water by a nucleophilic ring opening reaction confirmed by product analysis and
kinetic solvent isotope effects. A Brønsted plot for this reaction has two distinct correlations with βnuc = 0.52 and
0.65 for weak and strong bases, respectively, although a statistically corrected plot may indicate a single correlation.

Item Type: Article
Additional Information: UoA 18 (Chemistry) © The Royal Society of Chemistry 2002
Subjects: Q Science > QD Chemistry
Schools: School of Applied Sciences
School of Applied Sciences > Biomolecular Sciences Research Centre
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Depositing User: Briony Heyhoe
Date Deposited: 16 Oct 2007
Last Modified: 12 Jan 2011 12:26
URI: http://eprints.hud.ac.uk/id/eprint/445

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