• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1241-1255
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• 2002

Series of m- and p-substituted benzyl derivatives of pyrrole, tetramethyl 1-benzyl-3a,7a-dihydroindole-2,3,3a,4-tetracarboxylate, and trimethyl 1-benzylindole-2,3,4-tricarboxylate were prepared and their 13C NMR spectra were obtained in 0.1 M solutions of chloroform-d. Both single substituent parameter and dual substituent parameter analyses were carried out to correlate the substituent chemical shifts. The ${\beta}$ carbon of the indole series showed the most profound substituent effect dependence as well as the best correlation. The results are explained by the hyperconjugation of the benzyl methylene group.

• Bulletin of the Korean Chemical Society
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• v.21 no.1
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• pp.49-55
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• 2000

A series of m-, and p-substituted phenyl 2-thiophenecarboxylates and benzoates was prepared by the reaction of the corresponding acyl chlorides and phenols. Their $^1H$ and $^{13}C$ NMR chemical shifts were analyzed using single substituent parameter (S SP) and dual substituent parameter (DSP) methods. The relative aromaticity index of thiophene was estimated to be 0.92 from the plot of the chemical shift of the carbonyl carbons of the thienoyl esters against chemical shift of the carbonyl carbons of the benzoyl esters.

• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1525-1530
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• 2004

Mutagen X (MX) exists in our drinking water as the bi-products of chlorine disinfection. Being one of the most potent mutagen, it attracted much attention from many researchers. MX and its analogs are synthesized and modeled by quantitative structure activity relationship (QSAR) methods. As a result, factors affecting this class of compounds have been found to be steric and electrostatic effects. We tried to collect all the data available from the literature. With both CoMFA and CoMSIA various combinations of physiochemical parameters were systematically studied to produce reasonable 3-dimensional models. The best model for CoMFA gave $q^2$ = 0.90 and $r^2$ = 0.97, while for CoMSIA $q^2$ = 0.85 and $r^2$ = 0.94. So the models seem to be reasonable. Unlike previous result of CoMFA, in our case steric parameter alone gave the best statistics. Although the steric contribution was found to be the most important in both CoMFA and CoMSIA, steric parameter along with electrostatic parameter produced slightly better model in CoMSIA. Overall, steric contribution is clearly the most important single factor. However, when we compare chlorine and bromine substitution, chlorine substitution can be more mutagenic. This indicates that other factors such as electrostatic effect also influence the mutagenicity. From the contour maps, steric contribution seems to be focused on rather small area near C6 substituent of the furanone ring, rather than C3 substituent. Therefore the locality of steric contribution can play a significant role in mutagenicity.

• Bulletin of the Korean Chemical Society
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• v.17 no.11
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• pp.1056-1061
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• 1996

Solvolysis rates of 1-(4-methoxyphenyl)-l-phenyl-2,2,2-trifiuoroethyl chloride (1) and 1-(4-methoxyphenyl)-1-phenylethyl chloride (2) were measured in a variety of aqueous binary solvents, and the solvent effect was treated with the Grunwald-Winstein equation. The solvent effect on the solvolysis of 1 failed to give a single linear correlations using the ordinary Y or YCl, but exhibited the wide split pattern which could not be related to the solvent nucleophilicity. The improved correlations with YBnCl and extended dual-parameter treatment, log (k/k0)=mYCl+hI (mΔYΔ), were observed for the solvolysis of 1. These results suggest that the incipient cationic charge in the solvolysis of 1 is delocalized strongly into the aryl-rings in the transition state. While the solvent effect on the solvolysis of 2 is better correlated with Y or YCl than YBnCl but the linearity is not satisfactory. The correlation is comparably improved by the use of the extended Grunwald-Winstein equation, log (k/k0)=0.81YCl+0.26NOTs (R=0.994, SD=±0.12), indicating the cationic charge of reaction center of 2 was localized mostly in the transition state.

• Journal of the Korean Chemical Society
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• v.32 no.2
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• pp.135-143
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• 1988

The correlations between chromatographic parameters of monosubstituted benzenes and several physical parameters in reversed phase liquid chromatography were studied. The relationships between retention data and polarity index were investigated by plotting $log(log k'_S/k'_B)$ vs. $P'_S/P'_B$ which were relative retention and relative polarity index of monosubstituted benzenes with respect to benzene, respectively. The linear relationship between relative retention and polarity index was observed for the monosubstituted benzenes having polar group, while in case of those having nonpolar group, the good linearity was observed by combination with relative molecular weight i.e. $(P'_S/P'_B)/(MW_S/MW_B)$. Multivariant regression analysis, $a(P'_S/P'_B)+b(MW_S/MW_B)$+c did not give significantly better correlations compared to single variant analysis, $a[(P'_S/P'_B)/(MW_S/MW_B)]$+c, but multiple stepwise regression analysis was recommended when several physical parameters simultaneously were chosen. The best correlation between retention data for monosubstituted benzenes taken from the literature and substituent constant(${\pi}$), derived from hydrophobic parameter and the first order molecular connectivity index$(^1{\chi}^{\nu})$, was established for methanol/water mobile phase system. The larger the surface coverage of the stationary phase, the higher was the correlation coefficient between these two parameters and retention data.