Dependence of Some Ethylenic Jgem Values on Solvent and Concentration

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Abstract
Measurements of Jgem for α-chloroacrylonitrile (α-CAN) over wide concentration ranges in a number of nonaromatic solvents reveal a marked dependence on medium and concentration, and more limited studies on α-bromoacrylonitrile (α-BAN) give similar results. In addition, Jgem for five vinylic compounds appear to vary with solvent to a smaller, but statistically significant extent. The variation for a given solute with solvent follows the dielectric constant and is roughly proportional to the reaction field of the medium. In α-CAN it has also been established that the variation of Jgem and of the two chemical shifts, as concentration changes, are rather parallel. The practical and theoretical significance of these observations are discussed, and some of the possible factors involved are broached in qualitative terms.