Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Correlation of the Rates of Solvolysis of 4-Morpholinecarbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Kim, Ran (Department of Chemistry Education and Research Instituted of Natural Science, Gyeongsang National University) ;
  • Ali, Dildar (Institute of Biochemistry, University of Balochistan) ;
  • Lee, Jong-Pal (Department of Chemistry, Dong-A University) ;
  • Yang, Ki-Yull (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 : 2010.04.21
  • Accepted : 2010.05.19
  • Published : 2010.07.20
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Abstract

The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

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References

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