Abstract
†The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate (I) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the NT solvent nucleophilicity scale and the YCl solvent ionizing scale, with sensitivities towards changes in the scale having values of 1.42 ± 0.09 for l and 0.39 ± 0.05 for m, respectively. The activation enthalpies are ∆H ≠ = 12.3 to 14.5 kcal·mol ‒1 and the activation entropies are ‒28.2 to ‒35.5 cal·mol ‒1 ·K ‒1 , consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.
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