Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates

  • Ik-Hwan Um (Department of Chemsistry, Ewha Womans University) ;
  • Seok-Joo Lee (Department of Chemsistry, Ewha Womans University) ;
  • Hee-Sun Park (Department of Chemsistry, Ewha Womans University) ;
  • Dong-Sook Kwon (Department of Chemsistry, Ewha Womans University)
  • Published : 1994.02.20
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Abstract

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

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