Collect. Czech. Chem. Commun. 2004, 69, 2297-2314

Analysis of Substituent Effects in Naphthalene Skeleton

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 dissociation constants of 45 substituted 1- and 2-naphthoic acids in six organic solvents (methanol, ethanol, acetonitrile, dimethylformamide, dimethyl sulfoxide, pyridine) have been used to evaluate the substituent effects in the naphthalene skeleton. The dissociation constants data have been treated traditionally by using Dewar-Grisdale equation and the Taft DSP equation, and the alternative interpretation of substituent effects (AISE) method. Quantitative comparison of substituent effects and their transmission from different positions, combination of inductive and resonance effects from various positions, and effects of solvents are discussed. Best results are predominantly provided by the AISE. Substituent effects are stronger in the case of substituents affecting from ring of the naphthalene skeleton bearing carboxylic group than from ring not bearing carboxylic group, and there are no substantial differences between the individual positions of this ring. The contribution of resonance effects at 4α and 8β positions distinctly changes with the medium. Special quality of substituent H was found in comparison with other substituents presumably due their bulkier character. The principal component analysis (PCA) has been also applied to treat the mean dissociation constants using the single substituent property approach. The dissociation together with reactivity data for other naphthalene derivatives have been tested for comprehensive evaluation using PCA. There was found a large similarity of naphthalene reactivity data tested from the point of view of substituent effects.

Keywords: Naphthoic acids; Dissociation constants; Substituent effects; Solvent effects; Chemometrics; Naphthalenes; Carboxylic acids; Acidity; AISE.

References: 18 live references.