Collect. Czech. Chem. Commun. 2004, 69, 1479-1490

Effect of para Substitution on Dissociation of N-Phenylbenzenesulfonamides

Martin Mansfeld, Patrik Pařík* and Miroslav Ludwig

Department of Organic Chemistry, Faculty of Chemical Technology, University of Pardubice, nám. Čs. legií 565, 532 10 Pardubice, Czech Republic


The reaction of substituted anilines and benzenesulfonyl chlorides has been used to prepare 49 substituted N-phenylbenzenesulfonamides of general formula 4-X-C6H4SO2NHC6H4-Y-4'. Their purity was checked by elemental analysis. The substituents X and Y include H, CH3, CH3O, Cl, Br, CN, and NO2. The dissociation constants of all compounds were determined by potentiometric titration in methanol, acetonitrile, N,N-dimethylformamide, and pyridine. The obtained dissociation constants, pKHA, were correlated with various sets of substituent constants. It was found that the effects of substituents X and Y on the dissociation are best described by using the Hammett equation with σp constants and the Yukawa-Tsuno equation with σp- and σp constants, respectively. This result confirms the direct conjugation of Y substituent with the reaction centre. The explained variability using the additive model was above 96% in all the solvents used. The data also provided information about the transmission effect of the SO2 group. The average dissociation constants were further processed by the latent variables methods, principal components and conjugated deviations analyses.

Keywords: Sulfonamides; Dissociation constant; Substituent effects; Transmission effect; Chemometrics; Acidity; Hammett equation.

References: 19 live references.