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Correlation of the Rates of Solvolysis of Isopropyl Fluoroformate Using the Extended Grunwald-Winstein Equation

Title
Correlation of the Rates of Solvolysis of Isopropyl Fluoroformate Using the Extended Grunwald-Winstein Equation
Author
경진범
Keywords
Isopropyl fluoroformate; Addition-elimination; Grunwald-Winstein equation
Issue Date
2007-04
Publisher
KOREAN CHEMICAL SOC
Citation
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v. 28, No. 4, Page. 657-661
Abstract
The specific rates of solvolysis of isopropyl fluoroformate are well correlated using the extended Grunwald-Winstein equation, with a sensitivity (1) to changes in solvent nucleophilicity (N-T) and a sensitivity (m) to changes in solvent ionizing power (Y-Cl). The sensitivities (l = 1.59 +/- 0.16 and m = 0.80 +/- 0.06) toward changes in solvent nucleophilicity and solvent ionizing power, and the k(F)/k(Cl), values are very similar to those for solvolyses of n-octyl fluoroformate, suggesting that the addition step of an addition-elimination mechanism is rate-determining. For methanolysis, a solvent deuterium isotope effect of 2.53 is compatible with the incorporation of general-base catalysis into the substitution process. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.
URI
http://koreascience.or.kr/article/JAKO200702727090716.pagehttp://repository.hanyang.ac.kr/handle/20.500.11754/106385
ISSN
0253-2964; 1229-5949
DOI
10.5012/bkcs.2007.28.4.657
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ETC > 연구정보
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