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Correlation of the Rates of Solvolysis of Electron-Rich Benzoyl Chloride Using the Extended Grunwald-Wistein Equation

  • Oh, Hyunjung (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Choi, Hojune (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Park, Jong Keun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Yang, Kiyull (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Koo, In Sun (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University)
  • Received : 2013.06.04
  • Accepted : 2013.06.19
  • Published : 2013.09.20
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Abstract

The solvolysis rate constants of piperonyloyl chloride (1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale, $Y_{Cl}$ solvent ionizing scale, and I aromatic ring parameter with sensitivity values of $0.30{\pm}0.05$, $0.71{\pm}0.02$, and $0.60{\pm}0.04$ for l, m, and h, respectively. The solvent kinetic isotope effect values (SKIE, $k_{MeOH}/k_{MeOD}$ and $k_{50%MeOD-50%D2O}$) of 1.16 and 1.12 were also in accord with the values for the $S_N1$ mechanism and/or the dissociative $S_N2$ mechanism. The product selectivity values (S) for solvolysis of 1 in alcohol/water mixtures were in the range of 0.5 to 1.9, which is also consistent with the proposed unimolecular ionization mechanism.

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References

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