Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Correlation of the Rates on Solvolysis of 2,2,2-Trichloroethyl Chloroformate Using the Extended Grunwald-Winstein Equation

  • Koh, Han-Joong (Department of Science Education, Jeonju National University of Education) ;
  • Kang, Suk-Jin (Department of Science Education, Jeonju National University of Education)
  • Received : 2012.01.25
  • Accepted : 2012.02.27
  • Published : 2012.05.20
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Abstract

The solvolysis rate constants of 2,2,2-trichloroethyl chloroformate ($Cl_3CCH_2OCOCl$, $\mathbf{3}$) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $1.28{\pm}0.06$ and $0.46{\pm}0.03$ for $l$ and $m$, respectively. The activation enthalpies (${\Delta}H^{\neq}$) are 10.1 to 12.8 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) are -27.8 to -36.8 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect ($k_{MeOH}/k_{MeOD}$) of 2.39 is also in accord with $S_N2$ mechanism probably assisted by general-base catalysis.

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References

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