Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XLIII. Solvent Effect on Activation Parameters of Dehydrochlorination of 3-Chloro-3-methylbut-l-ene. Correlation Analysis of Solvation Effects

摘要

The influence of temperature on the rate of dehydrochlorination of 3-chloro-3-methylbut-1-ene in 17 aprotic and 13 protic solvents, v = k[C5H9Cl], was studied by the verdazyl method. In aprotic solvents, the electrophilicity, ionizing power, and cohesion of solvents decrease triangle open G~(not =) by increasing triangle openS~(not =). The nucleo-philicity and polarizability increase both triangle openH~(not =) and triangle openS~(not =) to equal extent and therefore do not affect triangle openG~(not +). In protic solvents, the solvent nucleophilicity increases triangle openH~(not =) to a greater extent than triangle openS~(not =), and the overall effect of the nucleophilic solvation is small and negative.