Collect. Czech. Chem. Commun. 2001, 66, 770-784

Substituent Effects on the Base-Catalysed Hydrolysis of Phenyl Esters of ortho-Substituted Benzoic Acids

Ingrid Bauerová and Miroslav Ludwig*

Department of Organic Chemistry, Faculty of Chemical Technology, University of Pardubice, Čs. Legií 565, CZ-532 10 Pardubice, Czech Republic


Fourteen model phenyl esters of 2-substituted benzoic acids were synthesised. Structures and purity of model compounds were confirmed by 1H and 13C NMR spectroscopy, as well as by HPLC and elemental analysis. Kinetics of base-catalysed hydrolysis of model phenyl esters occurring by the BAc2 mechanism were measured by UV spectrophotometry in 50% (v/v) aqueous dimethyl sulfoxide solutions at 25 °C under pseudo-first-order reaction conditions (c(NaOH) = 0.001-1.0 mol l-1). Linear relation between J-E and log kobs with the slope close to unity was found for all model compounds. Neither one-parameter nor multiparameter Hammett-type description of variability of experimental data obtained for phenyl esters of 2-substituted benzoic acids was found. Two groups (conjugating and non-conjugating) were created by division of ortho-substituents in ortho-position using the AISE theory, based on their interaction with the reaction centre.

Keywords: Esters; Benzoic acids; Base-catalysed hydrolysis; ortho-Effect; Substituent effects; Kinetics; Chemometrics; Hammett equation; AISE theory.

References: 34 live references.