Abstract
Solvolysis of acyclic mixed carboxylic–sulfonic anhydrides in hydroxylic solvents is known to involve displacement at the carbonyl carbon to produce a carboxylic acid (water as the nucleophile) and/or an ester (alcohol as the nucleophile) plus the anion of the sulfonic acid. Parallel solvolyses of the cyclic mixed anhydride 2-sulfobenzoic anhydride (structurally similar to phthalic anhydride but with one carbonyl group replaced by a sulfonyl group) involve expulsion from the carbonyl carbon of a sulfonate anion that remains attached as an ortho-substituent in the benzoic acid and/or benzoate ester produced. This complicates the choice of a solvent-ionising-power scale for use in an extended Grunwald–Winstein equation treatment. The YOTs scale, previously recommended as a good general purpose scale, is chosen and used in conjunction with the NT solvent nucleophilicity scale. An acceptable correlation is obtained, which is improved when the two solvents rich in the highly ionising 1,1,1,3,3,3-hexafluoro-2-propanol are excluded. As the solvent is varied, the sensitivities to the changes induced in the two scales are low, consistent with an early transition state, but their ratio has a value which is typical for a pathway involving addition–elimination, with addition rate-determining. Earlier reports, supporting aspects of the proposed mechanism, are reviewed.
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