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

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

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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.
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 which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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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