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http://dx.doi.org/10.5012/bkcs.2008.29.9.1747

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

Seong, Mi-Hye (Department of Chemistry and Applied Chemistry, Hanyang University)
Kyong, Jin-Burm (Department of Chemistry and Applied Chemistry, Hanyang University)
Kim, Dong-Kook (Department of Chemistry and Applied Chemistry, Hanyang University)
Kevill, Dennis N. (Department of Chemistry and Biochemistry, Northern Illinois University)
Publication Information
Bulletin of the Korean Chemical Society / v.29, no.9, 2008 , pp. 1747-1751 More about this Journal
Abstract
Reactions of n-propyl fluoroformate in a variety of pure and binary solvents have been studied at 40.0 {^{\circ}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 ${\pm}$ 0.17 and m = 0.96 ${\pm}$ 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.
Keywords
n-Propyl fluoroformate; Addition-elimination; Grunwald-Winstein equation; Leaving group effect
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