Correlation of the Rates of Solvolysis of 1-and 2-Naphthyl Chloroformates Using the Extended Grunwald-Winstein Equation

The specific rates of solvolysis of 1- naphthyl chloroformate (1-NaphOCOCl, I) and 2-naphthyl chloroformate (2-NaphOCOCl, 2) have been determined in a wide range of solvents at 2.0 and 10.0 degrees C. These give a satisfactory correlation over the full range of solvents when the extended (two-term) Grunwald-Winstein equation is applied. The sensitivities (1 and in-values) to changes in solvent nucleophilicity (N-T) and solvent ionizing power (Y-Cl) are similar to those reported previously for solvolysis of phenyl chloroformate, which has been suggested to proceed through an addition-elimination mechanism with the addition step being rate determining. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations were also compared with those previously reported for phenyl chloroformates and naphthoyl chlorides.This work was supported by the research fund of Hanyang University (HY-2009-N)