ORGANIC AND BIOLOGICAL SPECTROCHEMICAL STUDIES: XXIII. CONFORMATION OF THE p-DIMETHOXYBENZENE CATION RADICAL IN CONCENTRATED SULFURIC ACID

The electron spin resonance spectrum of the p-dimethoxybenzene cation radical in concentrated sulfuric acid is interpreted in terms of cis–trans isomerism. Empirical molecular orbital calculations support these assignments. The two isomers are found to possess slightly different "g" values, Δg (cis – trans) being ca. 1.8 × 10−5.Nuclear magnetic resonance and ultraviolet data show that the radical exists in equilibrium with the neutral non-radical species at room temperature, but that sulfonation occurs at higher temperatures. Nuclear magnetic resonance and electron spin resonance data of solutions of p-dimethoxybenzene in D2SO4 show that rapid exchange of the ring protons occurs.