QUANTITATIVE FORMULATION OF REACTIVITY IN TERMS OF SOLVENT AND SUBSTRATE PROPERTIES - SOLVOLYSIS OF TERT-BUTYL HALIDES IN HYDROXYLIC SOLVENTS

Experimental rate constant values for the solvolysis of tert-butyl chloride in 12 alcohols at 25-degrees-C are presented. These results, together with previous data, are well correlated through the linear solvation energy relationship log k = a0 + a1 g(eta) + a2 E(T)N + a3 C where g(eta) is a function of the refractive index, E(T)N 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(eta), E(T)N and C] and of the substrate [molar volume (V) and dipole moment (mu)] simultaneously was performed.