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Abstract
Abstract The effect of pressure on the formolysis of 1-(P-substituted benzyl) ethyl tosylates was investigated, and the activation volumes, ΔVo\eweq were estimated. The apparent values of activation volume were found to correlate nicely with σ*. Because the present substrates were believed to be formolyzed through two separate processes, anchimerically assisted (kΔ) and unassisted (ks), the apparent values of activation volume were partitioned into the corresponding activation volumes, ΔVΔ\eweq and ΔVs\eweq. The dependence of ΔVΔ\eweq and ΔVs\eweq on the substituents was examined, and the correlation between the mechanisms of solvolysis and ΔVΔ\eweq and ΔVs\eweq was discussed.
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