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

The specific rates of solvolysis of methyl fluoroformate have been measured at $40.0\;{^{\circ}C}$ in several hydroxylic solvents. Analysis with the extended Grunwald-Winstein equation leads to sensitivities toward changes in solvent nucleophilicity (l) of $1.33\;{\pm}\;0.10$ and toward changes in s...

Full description

Saved in:
Bibliographic Details
Published inBulletin of the Korean Chemical Society Vol. 30; no. 10; pp. 2408 - 2412
Main Authors Seong, Mi-Hye, Choi, Song-Hee, Lee, Yong-Woo, Kyong, Jin-Burm, Kim, Dong-Kook, Kevill, Dennis N
Format Journal Article
LanguageKorean
Published 2009
Subjects
Grunwald-Winstein equation
Solvent isotope effect
ddition-elimination
Methyl fluoroformate
Online AccessGet full text

Cover

More Information
Summary:The specific rates of solvolysis of methyl fluoroformate have been measured at $40.0\;{^{\circ}C}$ in several hydroxylic solvents. Analysis with the extended Grunwald-Winstein equation leads to sensitivities toward changes in solvent nucleophilicity (l) of $1.33\;{\pm}\;0.10$ and toward changes in solvent ionizing power (m) $0.73\;{\pm}\;0.06$. For methanolysis, a solvent deuterium isotope effect of 3.98 is compatible with the incorporation of general-base catalysis into the substitution process. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations are also compared with those previously reported for alkyl halogenoformate esters and mechanistic conclusions are drawn.
Bibliography:KISTI1.1003/JNL.JAKO200902727263648
ISSN:0253-2964
1229-5949