Correlation of the rates of solvolysis of benzoyl fluoride and a consideration of leaving-group effects

The specific rates of solvolysis of benzoyl fluoride have been determined at 25.0 degrees C in 37 pure and binary solvents. Together with seven values from the literature, these give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation is applied. The sensitivities to changes in solvent nucleophilicity and solvent ionizing power are very similar to those for octyl fluoroformate, suggesting that the addition step of an addition-elimination mechanism is rate determining. In the solvent-composition region where benzoyl chloride also shows bimolecular solvolysis, the appreciable k(Cl)/k(F) values are proposed as being primarily due to a more efficient ground-state stabilization for the fluoride.