Evidence for the existence of an electric field effect from the vinyl proton magnetic resonance spectra of 4-substituted styrenes

Abstract

Vinyl proton chemical shifts of styrene and six 4-substituted styrenes have been determined at infinite dilution in cyclohexane. It is shown that changes in the chemical shift difference of the β protons, Δ(δC − δB) can be accounted for by electric field effects. Reasonable values of the constant in the Buckingham equation of(−3.11 ± 0.50) × 10−12 and (−4.77 ± 0.83) × 10−12 are obtained from two different types of field effect calculations. Residual chemical shift changes for β protons after correction for electric field effects can be explained in terms of mesomeric and possibly inductive mechanisms. α-Proton chemical shift values cannot be satisfactorily rationalized. Small concentration effects are noted, usually resulting in high field shifts with increasing concentration. Previous results are reexamined in order to resolve a conflict in the literature.