Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The New Substituent Constants in the Excited States (II)

  • Sang-Chul Shim (Department of Chemistry, Korea Advanced Institute of Science and Technology) ;
  • Joon-Won Park (Lucky Central Research Institute) ;
  • Heui-Suk Ham (Department of Chemistry, Chunnam National University) ;
  • Jin-Soon Chung (Department of Chemistry, Chunnam National University)
  • Published : 1983.02.20
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Abstract

In order to standardize the ${\sigma}^*,\;{\rho}^*$ is taken as unity for the benzoic acids by analogy with the fact that ${\rho}$ of benzoic acids in the ground state is taken as unity. The $pK_{\alpha}^*$ of many benzoic acid derivatives are determined by UV spectroscopy and fluorescence spectral analysis whenever possible. The ${\sigma}^*$ constants are derived from the Hammett equation utilizing these $pK_{\alpha}^*$ values and the $pK_{\alpha}^*$ of the benozic acid derivatives showed better correlationship with ${\sigma}^*$ than ${\sigma},\;{\sigma}^+\;and\;{\sigma}^-$ as expected. From these ${\sigma}^*$ values, ${\rho}^*$ of the phenol derivatives was calculated to be 1.28. The new standardized ${\sigma}^*$ values are calculated from the $pK_{\alpha}^*$ values of phenols since more accurate and abundant data are available for phenols than the benzoic acid derivatives.

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References

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