Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Limitations of the Transition State Variation Model(5) Dual Reaction Channels for Solvolysis of Dansyl Chloride

  • Koo In Sun (Department of Chemical Education, Gyeongsang National University) ;
  • Lee Ocg-Kyeong (Department of Chemical Education, Gyeongsang National University) ;
  • Lee Ikchoon (Department of Chemistry, Inha University)
  • Published : 1992.08.20
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Abstract

Rate of solvolysis of dansyl chloride in aqueous binary mixtures of acetone, methanol and ethanol are reported. Kinetic solvent isotope effects in methanol and product selectivities in alcohol-water mixtures are also reported. Kinetic data are interpreted with the Grunwald-Winstein and Kivinen equations. The value of $k_{CH3OH}/k_{CH3OD}=1.76$ suggests that a general have catalyzed and/or an $S_AN$ pathway is operative in methanol, a less polar solvent. Rate-rate profiles for solvolysis of dansyl chloride in the aqueous binary media indicate a change in reaction channel from $S_AN$ (in less polar media) to $S_N2$ (in more polar media) mechanism.

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