Collect. Czech. Chem. Commun. 1996, 61, 1205-1214

Effects of Medium and Substituents on Dissociationof 4,4'-Disubstituted Bis(benzenesulfon)imides

Miroslav Ludwig and Pavel Štverka

Department of Organic Chemistry, Faculty of Chemical Technology, University of Pardubice, 532 10 Pardubice, Czech Republic


Ten 4,4'-disubstituted bis(arenesulfon)imides of the general formula XC6H4SO2NHSO2C6H4X have been synthesized and their structures confirmed by their 1H NMR spectra. Elemental analyses are presented for the compounds not yet described. The dissociation constants of these model substances have been measured potentiometrically in pyridine, dimethylformamide, methanol, ethanol, propylene carbonate, acetone, acetonitrile, 1,2-dichloroethane and tetramethylene sulfone. The pKHA values obtained have been correlated with three sets of the Hammett substituent constants and the results have been used to discuss the solvent and substituent effects on the dissociation of the compounds studied. Sulfonimides with electron-acceptor substituents behave as rather strong acids in some solvents (pyridine, dimethylformamide, methanol and ethanol), whereas normal substituent dependences are found in other solvents. The experimental data have also been interpreted with the help of the statistical methods based on latent variables. From the calculations it follows that only the first principal component, which correlates well with the substituent constant sets adopted, is statistically significant in describing the substituent effect on the acid-base process studied.

Keywords: Sulfonamides; Dissociation; Substituent; Solvent; Chemometrics.