Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Butane-2,3-dione Monoximate and 4-Chlorophenoxide: Origin of the α-Effect

  • Kim, Min-Young (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Min, Se-Won (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • Received : 2012.08.19
  • Accepted : 2012.10.02
  • Published : 2013.01.20
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Abstract

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

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References

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