Collect. Czech. Chem. Commun. 2005, 70, 198-222

Kinetic Study of Alkaline Hydrolysis of Substituted Phenyl Tosylates. XXII. Variation of Ortho Substituent Effect with Solvent

Vilve Nummert, Mare Piirsalu*, Marika Lepp, Vahur Mäemets and Ilmar Koppel

Institute of Chemical Physics, Tartu University, Jakobi 2, 51014 Tartu, Estonia


The second-order rate constants k (dm3 mol-1 s-1) for the alkaline hydrolysis of meta-, para-, and ortho-substituted phenyl tosylates 4-CH3C6H4SO2OC6H4-X in aqueous 0.5 M Bu4NBr have been measured spectrophotometrically in a wide temperature range. The log k values for ortho-substituted derivatives at various temperatures together with meta- and para-substituted derivatives were analyzed using the modified Fujita-Nishioka equation log km,p,ortho = c0 + c1(m,p,ortho)σ° + c2(ortho)σI + c3(1/T) + c4(m,p,ortho)(1/T)σ° + c5(ortho)(1/TI. In order to study the dependence of substituent effects, especially ortho inductive and resonance terms on different solvent parameters, the following equation was used: ∆log km,p,ortho = c0 + c1(m,p,ortho)σ° + c2(ortho)σI + c3E + c4Y + c5P + c6(m,p,ortho)Eσ° + + c7(m,p,ortho)Yσ° + c8(m,p,ortho)Pσ° + c9(ortho)EσI + c10(ortho)YσI + c11(ortho)PσI. ∆log k = log kX - log kH, σ° and σI, are the Taft polar and inductive substituent constants, E, Y and P, are the solvent electrophilicity, polarity and polarizability parameters, respectively. In data treatment ∆E = ES - EH2O, ∆Y = YS - YH2O, ∆P = PS - PH2O were used. The solvent electrophilicity was found to be the main factor responsible for changes in the ortho, para, and meta polar substituent effects with medium. The variation of the ortho inductive term with the solvent electrophilicity ES was found to be twice smaller than that for para substituents, while the ortho resonance term appeared to vary with solvent nearly similarly to that for para substituents. The ortho effect caused by the supplementary inductive effect from ortho position was found to disappear in a solvent whose electrophilic solvating power is comparable to pure DMSO (E ≈ 4).

Keywords: Esters; Sulfonates; Phenyl tosylates; Alkaline hydrolysis; Substituent effects; Ortho effects; Solvent effects; Kinetics.

References: 40 live references.