Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The Effect of Solvent on the $\alpha$-Effect(3): Nucleophilic Substitution Reactions of Aryl Acetates in $MeCN-H_2O$ Mixtures of Varying Compositions

  • Um Ik-Hwan (Department of Chemistry, Ewha Womans University) ;
  • Hahn Gee-Jung (Department of Chemistry, Ewha Womans University) ;
  • Lee Gwang-Ju (Department of Chemistry, Ewha Womans University) ;
  • Kwon Dong-Song (Department of Chemistry, Ewha Womans University)
  • Published : 1992.12.20
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Abstract

Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

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