Vinyl cations. Part 13. Secondary kinetic deuterium isotope effects in the solvolysis of ring-substituted β-styryl trifluoromethanesulphonates

Abstract
The β-kinetic deuterium isotope effects have been measured in the solvolysis of a series of ring-substituted β-styryl trifluoromethanesulphonates. At 75 °C in aqueous 80% ethanol for the parent compound, kH/kD= 1.45; for p-Cl, kH/kD= 1.74; for m-Cl, kH/kD= 1.61; for p-CF3, kH/kD= 1.64; for p-NO2, kH/kD= 1.71. Both the protio- and deuterio-series gave an excellent Hammett correlation with σ+(ρ–4.12 and –4.17, respectively). The products of solvolysis were the corresponding acetophenones and phenylacetylenes. The significance of these results is discussed.

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