Collect. Czech. Chem. Commun. 2001, 66, 1380-1392

Ortho Effect in Dissociation of Substituted N-Phenylbenzenesulfonamides

Jiří Nádvorník and Miroslav Ludwig*

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


Twenty-five 2,2'-disubstituted N-phenylbenzenesulfonamides (2-X-C6H4SO2NHC6H4-Y-2') were synthesised and their purity checked by elemental analysis. This set of model substrates involved all possible combinations of methoxy, methyl, hydrogen, chloro, and nitro substituents. The dissociation constants of the sulfonamides were determined by potentiometric titration in methanol, pyridine, dimethyl sulfoxide, N,N-dimethylformamide, acetone, and acetonitrile. The dissociation constants pKHA obtained were correlated with various sets of substituent constants describing electronic and steric effects of the substituents, and the statistically treated data were used to discuss the contribution of the substituent effects in the dissociation and the difference between the effects transmitted from the two rings. A linear regression model explaining 99% of the variability of experimental data in all the solvents has been found and discussed. Moreover, the experimental data were also interpreted by the methods using latent variables, the principal component analysis (PCA) and conjugated deviation analysis (CDA), and two latent variables were shown to be statistically significant in the description of dissociation. The first obviously describes common action of electronic and steric effects of substituents; the other probably concerns a combined effect of substituent and solvent on the position of acid-base equilibrium.

Keywords: Sulfonamides; Dissociation constants; ortho Effect; Chemometrics; Substituent effects; Solvent effects.

References: 19 live references.