• Bulletin of the Korean Chemical Society
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• v.2 no.2
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• pp.41-45
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• 1981

For solvolyses of benzenesulfonylchlorides we determined transfer enthalpies of transition states, and solvent (TFE + EtOH) and substituent effects on rates. We have used the More O'Ferrall plots to show that transition states variation caused by solvent and substituent changes is consistent with an associative $S_N2$ mechanism for the nucleophilic substitution reaction of benzenesulfonylchlorides.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.38-43
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• 1992

The Hammett's substituent constants were interpreted for substituted stilbenes by HMO method. The appropriate quantum chemical indices are chosen as independent contribution of the inductive and the resonance effects for substituent constants. It has been found that theoretical values, ${\sigma}_p{^{th}}$, defined as sum of the net charge, self atom polarizability and difference in HOMO energy between substituted- and unsubstituted-stilbenes, correlated with experimental Hammett's substituent constants. The dipole moments were found to be correlated with differences in ${\sigma}_p{^{th}}$ between two substituents for disubstituted stilbenes. It has been also found that transition optical spectra, ${\lambda}_{max}$ of the substituted stilbenes depend on difference between the HOMO and the LUMO energy as expected.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.279-283
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• 1984

${\beta}$-Substituent effect on the reactivity of retro-ene decarboxylation of but-3-enoic acid was investigated theoretically. It was found that charge effect is important not only through ${\pi}$-electron transfer as has been claimed to rationalize experimental results but also through polarization as found for the $CH_3$ substituent. The reactivity was not determined by the charge effect alone but the HOMO-LUMO energy gap was also found to affect the reactivity. In general it was confirmed that the greater the ${\pi}$-electron donating power of the substituent, the greater is the reactivity.

• The Journal of Natural Sciences
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• v.15 no.1
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• pp.47-56
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• 2005

The substituent dependence of geometric distortion through the two independent electronic substituent effects is analyzed for mono-substituted benzene derivatives of $C_{2v}$. Based on resonance structures, quantitative relationships expressing the resonance and field/inductive contribution terms in bond distortions are derived. The calculated field-effect parts of $C_{ipso}$_$C_{ortho}$ ring bonds increase and decrease compared to benzene for electropositive and electronegative substituents respectively. The nonbonded axial distance, $C_{ipso}$....$C_{para'}$ decreases for electronegative substituents and increases for electropositive substituents. As the electronegativity increases, the distance $C_{ortho}$....$C_{ortho'}$ increases. With the $\pi$-donors, $C_{meta}$....$C_{meta'}$ nonbonded distances are shorter compared to the ones of benzene, and for $\pi$-acceptors, the are longer. Our model based on valence bond approach predicts that the average bond length determined the area of ring, and the sum of the angles <$C_{ortho}$_$C_{ispo}$_$C_{ortho}$ and <$C_{meta}$_$C_{para}$_$C_{meta}$ determines the axial distance.

• Journal of the Korean Chemical Society
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• v.19 no.6
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• pp.449-453
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• 1975

Substituent effect of the leaving groups of the reaction of benzyl arenesulfonate with dimethylanilines in acetone at $35^{\circ}C$ was obtained with the following results. 1. Substituent effect of the leaving groups was not variable when changed from pyridine to N,N-dimethylaniline in nucleophile 2.In acetone, the Hammett ${\sigma}$ constant of p-MeO of the leaving group was -0.35. 3. The weaker the nucleophilicity in dimethylaniline, the stronger the movement of electron from N to C, and the cleavage of the C${\ldots}$0 bond in transition state proceeds.

• Journal of the Korean Chemical Society
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• v.50 no.3
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• pp.183-189
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• 2006

A series of substituted styryl 4-methoxy-1-naphthyl ketones [(2E)-1-(4-methoxy-1-naphthyl)-3-phenyl-2-propen-1-ones] were synthesized using facile method of microwave assisted condensation reaction. The yield of chalcones is more than 90%. They are characterized by their physical constants, micro analysis, infrared (KBr, 4000-400 cm？1) and NMR both 1H and 13C spectral data. From infrared spectra, the s-cis and s-trans stretching vibrations of carbonyl group, from NMR spectra the ethylenic proton and carbon chemical shifts (ppm) are assigned. These spectral data are correlated with various Hammett substituent constants. From the results of statistical analysis the effect of substituents on CO, ？ and ？ proton and carbons are explained.

• Bulletin of the Korean Chemical Society
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• v.19 no.5
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• pp.527-530
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• 1998

This paper presents the electrochemistry and molecular orbital (MO) picture of a series of conformationally-restricted thioxantone derivatives. A series of $C_2-substituted$ thioxanthones were examined to probe the electronic influence of the substituent on the electrooxidation and electroreduction sites (i.e., on the electron densities at the 10-and 9-positions), respectively. In the presence of "electrophoric" groups such as C=O and S, characteristic electrochemical reduction and oxidation responses are observed. The electrochemical reaction was diffusion-controlled, because the $I_p/{\upsilon}^{1/2}$ ratio was constant for the anodic and cathodic wave of thioxantone derivatives. These substituent effects are presented in terms of correlations of oxidation (or reduction) potentials with the highest occupied molecular orbital (HOMO), or lowest unoccupied molecular orbital (LUMO) energies, respectively. There is good correlation between energies of the HOMO vs. $E_{pa}^{(+)}$ and energies of the LUMO vs. $E_{pc}^{(-)}$. Frontier Molecular Orbital (FMO) is changed by the functional group of thioxanthones. FMO energy level was offered us the information about the electron transfer direction, and the coefficient of FMO was offered the information about the electron transfer position. Sulfur atom has an important effect on oxidation potential, $E_{pa}^{(+)}$ and the carbonyl carbon has an important effect on reduction potential, $E_{pc}^{(-)}$. Therefore we were appreciated that the contribution of sulfur atom for the $E_{pa}^{(+)}$ and HOMO energies is larger than the contribution of carbonyl group for the $E_{pc}^{(-)}$ and LUMO energies.

• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.783-785
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• 1997

• Bulletin of the Korean Chemical Society
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• v.8 no.4
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• pp.348-349
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• 1987

• Journal of the Korean Chemical Society
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• v.20 no.5
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• pp.391-397
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• 1976

Substituent effects of leaving group in benzylarenesulfonates solvolysis have been carried out in 10∼50% water-acetone mixtures by electric conductivity method. Results of solvent effects, substituent effects and variable rate difference of water contents, show that $S_N1$ character almost predominates through the substituents, though p-MeO favors more or less $S_N2$ character in low water contents.