Anomalous electrochemical and electron spin resonance properties of some biologically relevant methoxyl-substituted quinones

Abstract

The proton hyperfine coupling constants for the family of methoxyl-substituted semiquinones in aqueous solution have been determined by electron spin resonance (ESR) spectroscopy. These data and the electrochemical midpoint potentials for the corresponding series of substituted quinone/hydroquinone couples are discussed. Neither the additivity principle describing quinoidal hyperfine coupling constants nor the Hammett substituent relationship predicting electrochemical behavior are obeyed by these methoxyl-substituted quinones. It is shown, however, that the experimental data can be rationalized in terms of neighboring group interactions that occur between adjacent methoxyl substituents. Such perturbations apparently lead to a breakdown of hyperconjugation between the electronic bonding structure of the quinone ring and the methyl group of the methoxyl moiety. It is pointed out that ubiquinone is a dimethoxyl compound whose properties are determined by such neighboring group interactions. This observation may have important consquences for the fabrication of ubiquinone analogs and quinone-based drugs.