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 nuc , 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 nuc , 0.56 ± 0.05 is obtained with n-nonanoyloxybenzenesulfonate. This increase in nuc 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.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.