Collect. Czech. Chem. Commun. 1997, 62, 913-924

Chemometric Analysis of Substituent Effects. XI. Solvent Effects on Dissociation of 2,6-Disubstituted Benzoic Acids

Jiří Kulhánek and Oldřich Pytela

Department of Organic Chemistry, University of Pardubice, 532 10 Pardubice, Czech Republic


Eleven symmetrically 2,6-disubstituted benzoic acids (with the following substituents: OCH3, OC2H5, OC3H7, OCH(CH3)2, OC4H9, CH3, F, Cl, Br, I, and NO2) have been synthesized and their dissociation constants measured potentiometrically in methanol, ethanol, propan-1-ol, propan-2-ol, butan-2-ol, acetone, dimethyl sulfoxide, dimethylformamide, acetonitrile, pyridine, and 1,2-dichloroethane. The experimental data obtained have been analyzed from the point of view of solvent effects on acidity of the individual derivatives. Different behaviour found with benzoic acid and the disubstituted derivatives in protic solvents is due to changes in solvation. The different character of solvation of benzoic acid and the disubstituted derivatives depends on the type of substitution, being manifested only in 2,6-disubstituted benzoic acids. The graphical analysis has shown a distinct trend in the increase of magnitude of deviation of the point of benzoic acid in the series: propan-2-ol, butan-2-ol, propan-1-ol, ethanol, methanol. This order correlates with the steric demands of carbon chain of the alcohols used. The abnormal behaviour of benzoic acid in the dissociation in these alcohols as compared with that of its 2,6-disubstituted derivatives is due to the different extent of solvation of the reaction centre caused by steric hindrance. Against the expectation, benzoic acid appears to be a weaker acid in protic solvents, whereas its alkoxy derivatives are stronger acids. The solvation also minimizes the inductive effect of alkoxy groups in the symmetrically 2,6-disubstituted derivatives. In aprotic solvents the acidity of 2,6-dialkoxybenzoic acids is also increased, in this case as a result of sterically forced deviation of the reaction centre and/or the substituents out of the plane of benzene ring.

Keywords: Substituent effects; ortho Effect; Solvation; Dissociation constants.