Nucleophilic substitutions in mixed solvents. Part II. Acid chlorides and alcohols in carbon tetrachloride

Abstract

By comparing the rate constant of the reaction of octanoyl chloride with n-octanol monomers in carbon tetrachloride with the rate constant for the corresponding reaction with alcohol trimers, the specific solvation energy of the transition state is found. The rates of the reactions between ethanol and acid chlorides in carbon tetrachloride are reduced by the addition of the polar molecules, alkyl bromides, n-hexyl fluoride, and acetone. The decrease in rate produced by acetone is related to the decrease in concentration of self-associated alcohol. These results are discussed in terms of a specifically solvated transition state formed by interaction of the acid chloride with associated groups of the alcohol.