Transfer of a positively charged acyl group between substituted phenolate ion nucleophiles: The Bronsted beta for the calibrating equilibrium for N-methylisonicotinyl (4-carbonyl-N-methylpyridinium) transfer

Colthurst, Matthew J. and Nanni, Matilde and Williams, Andrew (1996) Transfer of a positively charged acyl group between substituted phenolate ion nucleophiles: The Bronsted beta for the calibrating equilibrium for N-methylisonicotinyl (4-carbonyl-N-methylpyridinium) transfer. Journal of the Chemical Society-Perkin Transactions 2 (11). pp. 2285-2291. ISSN 0300-9580. (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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Official URL
http://dx.doi.org/10.1039/P29960002285

Abstract

Rate constants have been measured for the reaction of substituted phenolate ions with aryl acetate esters and with aryl N-methylisonicotinate esters dagger. in aqueous solution. A new method is demonstrated for determining beta(eq) for group transfer from 4-nitrophenyl esters; it employs the rate constant for the reaction of 2,6-difluorophenolate ion with substituted phenyl ester as a surrogate for the reactivity of the 4-nitrophenolate ion and yields beta(eq) = 1.55 for the N-methylisonicotinyl transfer reaction. The Bronsted-type plot of the rate constant for phenolate ion attack on 4-nitrophenyl N-methylisonicotinate is linear over a range of pK(a) values from 5.5 to 10 and provides good evidence for a concerted displacement mechanism for this reaction. The reactivity of the N-methylisonicotinate esters to phenolate ions is some 300 times larger than that of the corresponding acetate esters but the larger B-nuc value (0.90 compared with 0.74) suggests a 'later' transition structure. Calibration of the beta values with the corresponding beta(eq) gives a Leffler alpha(nuc) = 0.58 and 0.42 for N-methylisonicotinate and acetate respectively, which contrasts with the order expected from reactivity-selectivity. The tighter transition structure indicated by comparison of these alpha values is explained by a less favourable acylium ion in the case of the N-methylisonicotinyl transfer reaction.

Item Type: Article
Subjects: Q Science
Q Science > QD Chemistry
Divisions: Faculties > Science Technology and Medical Studies > School of Physical Sciences
Depositing User: M.A. Ziai
Date Deposited: 15 May 2009 08:07
Last Modified: 25 Jun 2014 13:21
Resource URI: https://kar.kent.ac.uk/id/eprint/18885 (The current URI for this page, for reference purposes)
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