Bulletin of the Korean Chemical Society

  • 제34권8호
  • /
  • Pages.2455-2460
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  • 2013
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Structure-Reactivity Correlations in Nucleophilic Displacement Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Z-Substituted-Phenoxides

  • Son, Yu-Jin (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Kim, Eun-Hee (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Kang, Ji-Sun (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • 투고 : 2013.05.20
  • 심사 : 2013.05.22
  • 발행 : 2013.08.20
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초록

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-$ClPhO^-$) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}X=0.89$ and r = 0.58. The Br${\o}$nsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.76$. The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4-$ClPhO^-$) is also linear with ${\beta}_{lg}=-0.72$. The Hammett plot correlated with ${\sigma}^-$ constants for the reactions of 5a-5d results in a much better linear correlation than that correlated with ${\sigma}^o$ constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.

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피인용 문헌

  1. The α-Effect in Nucleophilic Substitution Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Butane-2,3-dione Monoximate vol.34, pp.10, 2013, https://doi.org/10.5012/bkcs.2013.34.10.2877