Bulletin of the Korean Chemical Society

  • 제16권3호
  • /
  • Pages.277-281
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  • 1995
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Mechanistic Significances of the Reactivity-Selectivity Principle

  • 발행 : 19950300
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초록

The relationship between the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$ and validity of the reactivity-selectivity principle (RSP) has been derived: RSP is valid when W = ${\rho}i(0){\cdot}{\rho}j(0)/{\rho}ij$ is negative. The analysis of 100 reaction series indicated that for normal SN2 reactions involving variations of substituents in the nucleophile (X) and in the substrate (Y) RSP is valid only for a dissociative type for which ${\rho}Y(0)$ is negative, whereas for the acyl transfer reactions with rate-limiting breakdown of the tetrahedral intermediate RSP is valid in general for all substituent changes, X, Y and/or Z (substituent on the leaving group). The trends in the validity of RSP for certain types of reaction can be useful in supplementing the mechanistic criteria based on the signs of ${\rho}i(0)$, ${\rho}j(0)$ and ${\rho}ij$.

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참고문헌

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피인용 문헌

  1. Nucleophilic substitution reactions of cinnamoyl chlorides with anilines in acetonitrile and acetonitrile–methanol mixtures vol.1995, pp.12, 1995, https://doi.org/10.1039/p29950002257
  2. Nucleophilic Substitution Reactions of Thiophenyl 4-Nitrobenzoates with Pyridines in Acetonitrile vol.64, pp.13, 1995, https://doi.org/10.1021/jo990115p
  3. Kinetics and mechanism of the aminolysis of thiophenyl methylacetates in acetonitrile vol.32, pp.8, 1995, https://doi.org/10.1002/1097-4601(2000)32:8<485::aid-kin6>3.0.co;2-x
  4. Kinetics and Mechanism of the Pyridinolysis of Aryl Cyclobutanecarboxylates in Acetonitrile vol.23, pp.5, 1995, https://doi.org/10.5012/bkcs.2002.23.5.715
  5. Kinetics and Mechanism of the Aminolysis of Phenacyl Bromides in Acetonitrile. A Stepwise Mechanism with Bridged Transition State vol.24, pp.7, 2003, https://doi.org/10.5012/bkcs.2003.24.7.993
  6. Effects of substituents on activation parameters in SN2 reactions at aliphatic carbon in solution vol.23, pp.5, 2010, https://doi.org/10.1002/poc.1634
  7. Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile vol.32, pp.5, 1995, https://doi.org/10.5012/bkcs.2011.32.5.1539
  8. Towards mechanisms of bimolecular nucleophilic reactions in solution—probing the variation of the activation parameters in the reactions of aromatic compounds vol.25, pp.4, 1995, https://doi.org/10.1002/poc.1912
  9. Enthalpy–Entropy Correlations in Reactions of Aryl Benzoates with Potassium Aryloxides in Dimethylformamide vol.45, pp.4, 2013, https://doi.org/10.1002/kin.20763