Corrrelation of the specific rates of solvolysis of ethyl fluoroformate using the extended Grunwald-Winstein equation

The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 degrees 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 N(T) solvent...

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Bibliographic Details
Published in:International journal of molecular sciences 2009-03, Vol.10 (3), p.929-941
Main Authors: Seong, Mi Hye, Kyong, Jin Burm, Lee, Young Hoon, Kevill, Dennis N
Format: Article
Language:English
Subjects:
Carbon
Ethanol
Fluorine - chemistry
Formates - chemistry
Kinetics
Ratios
Solvents
Solvents - chemistry
Temperature
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Summary:The specific rates of solvolysis of ethyl fluoroformate have been measured at 24.2 degrees 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 N(T) solvent nucleophilicity scale and the Y(Cl) solvent ionizing power scale, and the k(F)/k(Cl) 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.
ISSN:1422-0067
1661-6596
1422-0067
DOI:10.3390/ijms10030929