Quantitative formulation of reactivity in terms of solvent and substrate properties. Solvolysis of tert-butyl halides in hydroxylic solvents

Abstract

Experimental rate constant values for the solvolysis of tert-butyl chloride in 12 alcohols at 25 °C are presented. These results, together with previous data, are well correlated through the linear solvation energy relationship log k=a0+a1 g(η)+a2ENT+a3C where g(η) is a function of the refractive index, ENT is the normalized Dimroth and Reichardt parameter and C is the solvent cohesive energy density. The same is true for tert-butyl bromide and iodide.A statistical treatment relating the experimental values of the solvolytic rate constants of the three halides in the same set of hydroxylic solvents (water, 8 monoalcohols and 10 dialcohols) to the properties of the solvents [g(η), ENT and C] and of the substrate [molar volume (V) and dipole moment (µ)] simultaneously was performed.