Bulletin of the Chemical Society of Japan · 1973 · 30 citations · 17 references
Natural SciencesChemistryOrganic ChemistryPhysical ChemistryHeterocycle SynthesisHeterocyclic ChemistryHeterocyclic CompoundsSubstituent EffectsSulfur ChemistrySulfur CompoundsHeterocyclic ReactivityPhenyl Ring Substitution EffectsRing Sulfur SubstitutionSulfur Containing Organic Compounds
Abstract The proton chemical shifts of the vinyl group in ring-substituted phenyl vinyl ethers (PVE) and sulfides (PVS) were measured and related to the Hammett σ constants. It was found that the ρ value for the β-trans proton of PVS, −0.448 τ⁄σ, is greater in magnitude than that of PVE, −0.378 τ⁄σ, in contrast to the tendency reported for the methyl hydrogens in anisole and thioanisole. The results can best be explained in terms of the concept of the through-conjugative (pπ-dπ-pπ) behavior of the sulfur atom interposed between two unsaturated groups.
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