• Bulletin of the Korean Chemical Society
• /
• 제23권9호
• /
• pp.1241-1255
• /
• 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
• /
• 제21권1호
• /
• pp.49-55
• /
• 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
• /
• 제25권10호
• /
• pp.1525-1530
• /
• 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
• /
• 제17권11호
• /
• pp.1056-1061
• /
• 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.

• 대한화학회지
• /
• 제32권2호
• /
• pp.135-143
• /
• 1988

역상 액체크로마토그래피에서 벤젠 일치환체들의 머무름 메카니즘과 머무름예측을 연구하기 위하여 크로마토 그래피 파라미터로 극성지표(P') 분자량(MW), 치환기 상수(${\pi}$ ) 및 분자간 연결지수$(^1{\chi}^{\nu})$를 머무름 데이터와 관련지어 상관관계를 조사하였다. 벤젠을 기존으로 하여 각 치환체의 크기인자와 비인 상대적 머무름$(log k'_S/k'_B)$과 각 치환체의 극성의비 $(P'_S/P'_B)$ 사이에는 상관관계가 있다. 치환기가 극성인 치환체들은 상관관계가 비교적 좋았으나 비극성 치환기를 갖는 치환체들은 분자량을 함께 고려함으로써 좋은 상관관계를 얻을 수 있다. 또한 상대적 머무름과 극성인자 및 분자량의 상관관계를 다변수 회귀분석으로 구하였다. 문헌적 머무름 자료와 소수성 파라미터로부터 유도된 치환기 상수(${\pi}$)와 분자간 연결지수$(^1{\chi}^{\nu})$ 간에는 메탄올의 이동상에서 가장 좋은 상관관계를 얻었다. $C_{18}$ 컬럼의 미반응된 실란올 기를 끝막음(end capping) 시키지 않은 컬럼에서는 이러한 상관관계가 감소되었다. 벤젠 일치환체들의 머무름과 관련지어 고려할 수 있는 파라미터는${\pi}$, P', $(^1{\chi}^{\nu})$ 및 MW 순으로 그 관련성이 감소됨을 알았다.