Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Fluoroformate and a Consideration of Leaving Group Effects

Abstract

Reactions of n-propyl fluoroformate in a variety of pure and binary solvents have been studied at 40.0 o C. The extended (two-term) Grunwald-Winstein equation has been applied to the specific rates of solvolysis of npropyl fluoroformate. The sensitivities (l = 1.80 ± 0.17 and m = 0.96 ± 0.10) to changes in solvent nucleophilicity and solvent ionizing power and the k F /k Cl values are similar to those for solvolyses of n-octyl fluoroformate over the full range of solvents, suggesting that the addition step of an addition-elimination mechanism is ratedetermining. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.