Structure-reactivity correlation for reactions of peroxide anion nucleophiles with substituted acyloxybenzenesulfonate bleach activators

Davies, Martin, Foggo, Steven and Paradis, Paul (1998) Structure-reactivity correlation for reactions of peroxide anion nucleophiles with substituted acyloxybenzenesulfonate bleach activators. Journal of the Chemical Society. Perkin Transactions 2 (6). pp. 1381-1383. ISSN 0300-9580

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Official URL: http://dx.doi.org/10.1039/A800832I

Abstract

Second-order rate constants are reported for the reaction between a series of esteric bleach activators with different acyl substituents, namely, acetyloxybenzenesulfonate, n-butanoyloxybenzenesulfonate, n-nonanoyloxybenzenesulfonate and isononanoyloxybenzenesulfonate, and a set of peroxide nucleophiles whose basicity ranges from below that of the oxybenzenesulfonate leaving group to above it. The results conform to a Brønsted-type relationship with βnuc, 0.42 ± 0.01 for acetyloxybenzenesulfonate, very similar to the value of 0.40 ± 0.01 for para-nitrophenyl acetate and a range of peroxide nucleophiles. A significantly larger value of βnuc, 0.56 ± 0.05 is obtained with n-nonanoyloxybenzenesulfonate. This increase in βnuc is interpreted in terms of steric and polar interactions between the acyl substituent and the attacking nucleophile. The reactivity of n-butanoyloxybenzenesulfonate is similar to that of n-nonanoyloxybenzenesulfonate whilst that of isononanoyloxybenzenesulfonate is less. These results are discussed in terms of the practical consequences for bleach activation and with regard to the mechanism of acyl transfer from esters to peroxides.

Item Type: Article
Subjects: F100 Chemistry
Department: Faculties > Health and Life Sciences > Applied Sciences
Depositing User: Becky Skoyles
Date Deposited: 02 Feb 2015 15:50
Last Modified: 24 Oct 2017 11:28
URI: http://nrl.northumbria.ac.uk/id/eprint/19776

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