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Int. J. Mol. Sci. 2011, 12(11), 7806-7817; doi:10.3390/ijms12117806

Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects

1
Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-do 426-791, Korea
2
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, USA
*
Author to whom correspondence should be addressed.
Received: 9 September 2011 / Revised: 21 October 2011 / Accepted: 31 October 2011 / Published: 10 November 2011
(This article belongs to the Special Issue Correlation Analysis Applied to Solvolysis Reactions)
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Abstract

The specific rates of solvolysis of isobutyl fluoroformate (1) have been measured at 40.0 °C in 22 pure and binary solvents. These results correlated well with the extended Grunwald-Winstein (G-W) equation, which incorporated the NT solvent nucleophilicity scale and the YCl solvent ionizing power scale. The sensitivities (l and m-values) to changes in solvent nucleophilicity and solvent ionizing power, and the kF/kCl values are very similar to those observed previously for solvolyses of n-octyl fluoroformate, consistent with the additional step of an addition-elimination pathway being rate-determining. The solvent deuterium isotope effect value (kMeOH/kMeOD) for methanolysis of 1 was determined, and for solvolyses in ethanol, methanol, 80% ethanol, and 70% TFE, the values of the enthalpy and the entropy of activation for the solvolysis of 1 were also determined. The results are compared with those reported earlier for isobutyl chloroformate (2) and other alkyl haloformate esters and mechanistic conclusions are drawn. View Full-Text
Keywords: i-butyl fluoroformate; Grunwald-Winstein equation; leaving group effect; addition-elimination; solvolysis i-butyl fluoroformate; Grunwald-Winstein equation; leaving group effect; addition-elimination; solvolysis
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Lee, Y.; Park, K.-H.; Seong, M.H.; Kyong, J.B.; Kevill, D.N. Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects. Int. J. Mol. Sci. 2011, 12, 7806-7817.

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