Paper
Correlation of the Rate of Solvolysis of Neopentyl Fluoroformate and a Consideration of Alkyl Haloformates in Solvolytic Reactions
- Authors:
- Dennis N. Kevill; Jin Burm Kyong; Kyoung-Ho Park; Mi Hye Seong
- Abstract
- The specific rates of solvolysis of neopentyl fluoroformate (NeopOCOF, 1) have been measured at 45.0 oC in pure and binary solvent mixtures. These results correlated well with the extended Grunwald-Winstein equation in all of the solvents except the four TFE-ethanol binary solvents. Leaving group effects (kF/kCl values) and sensitivity (l and m values) to changes in solvent nucleophilicity and solvent ionizing power are appreciably similar to those observed previously for the solvolyses of primary and secondary alky haloformates. This is consistent with the addition-elimination pathway as rate-determining. The kinetic solvent isotope effects (KSIEs, kMeOH/kMeOD) and activation parameters for the solvolyses of 1 were also determined. The results are compared with those reported earlier for neopentyl chloroformate (NeopOCOCl, 2) and other alkyl haloroformate esters.
- Keywords
- Neopentyl Fluoroformate; Grunwald–Winstein Equation; Leaving Group Effect; Solvolytic Reaction; Addition-Elimination Pathway
- StartPage
- 70
- EndPage
- 76
- Doi