Experimental Studies on the UV-Spectra of Several Substituted Pyridine N-Oxides and Conjugated Cationic Acids in Acetonitrile.docVIP

Molecules 1997, 2, 169- 175 molecules ISSN 1420-3049 Experimental Studies on the UV-Spectra of Several Substituted Pyridine N-Oxides and Conjugated Cationic Acids in Acetonitrile Lech Chmurzynski Department of Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk, Poland Tel.: +48-58-415271; Fax: +48-58-410357 (lesiu@sun1.chem.univ.gda.pl) Received: 2 June 1997 / Accepted: 24 August 1997 / Published: 15 November 1997 Abstract: The ultraviolet spectra of heterocyclic N-oxides of pyridine N-oxide series and the conjugated cationic acids (simple cations of protonated N-oxides) in acetonitrile as the representative of polar aprotic solvents, were determined. The obtained spectra of N-oxides studied (mainly tri-substituted pyridine N-oxides) and their cations obtained by the protonation of free N-oxides by the excess of perchloric acid, have been collected and discussed. Taking into account the spectroscopic results, a scheme of acid-base equilibria in polar aprotic solvents has been discussed. The influence of the traces of water on acid-base equilibria in non- aqueous media has been stressed. Keywords: UV spectra, pyridine N-oxides, cationic acids, perchloric acid, acetonitrile. Introduction BHB+ [6,7]. The hydrogen bond in homocomplex cation is exceptionally short, as revealed by X-ray crystallography [8], which results in its exceptionally high strength, leading It is well known [1-5] that the derivatives of pyridine N-oxide in polar aprotic solvents such as acetonitrile, in to the presence of a considerable amount of addition to proton-exchange equilibria with the solvent leading to the formation of simple BH cations, Eq. (1), also form hydrogen-bonded complexes containing two homoconjugated cations even in solvents with relatively high dielectric constants [1]. For this reason, simple and complex perchlorates seem to be good sources of simple and homocomplex cat