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Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation
Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-do 426-791, Korea
Department of Food and Biotechnology, Hanseo University, Seosan, ChungNam, 356-706, Korea
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA
* Authors to whom correspondence should be addressed.
Received: 15 February 2009; in revised form: 27 February 2009 / Published: 2 March 2009
Abstract: The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 °C in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation is applied. The sensitivities to changes in the NT solvent nucleophilicity scale and the YCl solvent ionizing power scale, and the kF/kCl values are very similar to those for solvolyses of n-octyl fluoroformate, consistent with the addition step of an addition-elimination pathway being rate-determining. For methanolysis, a solvent deuterium isotope effect of 3.10 is compatible with the incorporation of general-base catalysis into the substitution process. For five representative solvents, studies were made at several temperatures and activation parameters determined. The results are also compared with those reported earlier for ethyl chloroformate and mechanistic conclusions are drawn.
Keywords: Ethyl fluoroformate; addition–elimination; Grunwald–Winstein equation; solvent isotope effect
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Seong, M.H.; Kyong, J.B.; Lee, Y.H.; Kevill, D.N. Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation. Int. J. Mol. Sci. 2009, 10, 929-941.
Seong MH, Kyong JB, Lee YH, Kevill DN. Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation. International Journal of Molecular Sciences. 2009; 10(3):929-941.
Seong, Mi Hye; Kyong, Jin Burm; Lee, Young Hoon; Kevill, Dennis N. 2009. "Corrrelation of the Specific Rates of Solvolysis of Ethyl Fluoroformate Using the Extended Grunwald-Winstein Equation." Int. J. Mol. Sci. 10, no. 3: 929-941.