Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A Mechanistic Study on Nucleophilic Substitution Reactions of Aryl Substituted Benzenesulfonates with Anionic Nucleophiles

  • Um Ik-Hwan (Department of Chemistry, Ewha Womans University) ;
  • Lee Seok-Joo (Department of Chemistry, Ewha Womans University) ;
  • Kim Jung-Joo (Department of Chemistry, Ewha Womans University) ;
  • Kwon Dong-Sook (Department of Chemistry, Ewha Womans University)
  • Published : 1994.06.20
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Abstract

Second-order rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates $(1,\;X-C_6H_4SO_2-OC_6H_4-Y)$ with aryloxides $(Z-C_6H_4O^{-})$ and ethoxide $(EtO^-)$ in absolute ethanol at $25^{circ}C$. The nucleophilicity of aryloxides increases with increasing electron donating ability of the substituent (Z) on aryloxides, and results in a good Hammett correlation with $\sigma^{-}$ constant. The reactivity of 1 toward aryloxides and ethoxide shows also significant dependence on the electronic nature of the substituent X and Y. Large positive ${\sigma}_{acyl}$ values have been obtained for the reaction of 1 with phenoxide and ethoxide, indicating that the leaving group departure is little advanced at the transition-state of the rate-determining step. This has been further supported from the fact that ${\sigma}^-$ constant gives extremely poor Hammett correlation, while ${\sigma}^0$ does reasonably good correlation for the reaction of 1 with ethoxide. Thus, the present sulfonyl-transfer reaction is proposed to proceed via a ratedetermining attack of nucleophile to the sulfur atom of 1 followed by a fast leaving group departure.

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References

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