Studies of reactions within molecular complexes: alkaline hydrolysis of substituted phenyl benzoates in the presence of xanthines

Pirinccioglu, N. and Williams, A. (1998) Studies of reactions within molecular complexes: alkaline hydrolysis of substituted phenyl benzoates in the presence of xanthines. Journal of the Chemical Society-Perkin Transactions 2 (1). pp. 37-40. ISSN 0300-9580. (The full text of this publication is not available from this repository)

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Official URL
http://dx.doi.org/10.1039/a705499h

Abstract

Complexation with caffeine and theophylline-7-acetate depresses the rate of alkaline hydrolysis of substituted phenyl benzoates and is consistent with the formation of molecular complexes with 1 : 1 stoichiometry between the hosts and esters; stacking of the xanthines is excluded as an explanation in the range of concentrations studied. Bronsted-type correlations have been determined for the rate and complexation constants and for the transition-state binding constants, Development of effective charge in the transition state of the reactions in bulk solvent is slightly less than that in the host-ester complex, consistent with a similar electronic environment in both states, The negative Bronsted beta values for K-s indicate that the interactions between ester and hosts involve electron donation to the host from the ester, Inhibition of hydrolysis is attributed to repulsion of the hydroxide ion from the host-ester complex by the extra hydrophobicity engendered by the xanthine host, as well as by the weaker binding of the transition state to the host compared with that in the host-ester complex.

Item Type: Article
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Science Technology and Medical Studies > School of Biosciences
Depositing User: M.A. Ziai
Date Deposited: 28 Mar 2009 02:11
Last Modified: 28 Mar 2009 02:11
Resource URI: http://kar.kent.ac.uk/id/eprint/17498 (The current URI for this page, for reference purposes)
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