• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3355-3360
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• 2011

The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $-15.0^{\circ}C$. The studied substrate of 1,2-phenylene phosphorochloridate is cyclic five-membered ring of phosphorus ester, and the anilinolysis rate of 1 is much faster than its acyclic analogue (4: ethyl phenyl chlorophosphate) because of extremely small magnitude of the entropy of activation of 1 compared to 4. The Hammett and Bronsted plots exhibit biphasic concave upwards for substituent X variations in the nucleophiles with a break point at X = 3-Me. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) change from secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines to primary normal ($k_H/k_D$ > 1) with the weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the transition state (TS) variation from a predominant backside attack to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. The primary normal DKIEs are substantiated by a hydrogen bonded, four-center-type TS.

• Molecular & Cellular Toxicology
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• v.5 no.1
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• pp.14-22
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• 2009

In vitro cytotoxicity of 23 alkyl phenols (APs) on human cervical cancer cell lines (HeLa) was determined using the lactate dehydrogenase (LDH) cytotoxicity assay. Two different sets of descriptors were used to construct the calibration model based on Genetic Algorithm-Multiple Linear Regression (GA-MLR) based on the experimental data. A statistically robust Structure-Activity Relationships (QSAR) model was achieved ($R^2$=95.05%, $Q^2_{LOO}$=91.23%, F=72.02 and SE= 0.046) using three Dragon descriptors based on Me (0D-Constitutional descriptor), BELp8 (2D-Burden eigenvalue descriptor) and HATS8p (3D-GETAWAY descriptor). However, external validation could not fully prove its validity of the selected QSAR in characterization of the cytotoxicity of APs towards HeLa cells. Nevertheless, the cytotoxicity profiles showed a finding that 4-n-octylphenol (4-NOP), 4-tert-octyl-phenol (4-TOP), 4-n-nonylphenol (4-NNP) had a more potent cytotoxic effect than other APs tested, inferring that increased length and molecular bulkiness of the substituent had important influence on the LDH cytotoxicity.

• Journal of the Korean Chemical Society
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• v.40 no.12
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• pp.711-718
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• 1996

The relationship between chemical structure and antifungal activity of benzene ring substituents of 1-phenylpyrrolidine-2,5-diones is studied by testing of model compounds and use of conformational data. The analysis revealed a number of structural features as essential for the antifungal effect: (1) the presence of an intact-NCO group and benzene moiety; (2) the distance between para substituents and the N atom within the 5.318∼5.320 ${\AA}$ range; (3) the distance between substituent X3 and X5 in the interval 5.437∼6.072 ${\AA}$ for the active analogues. And other parameters were discussed.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.621-625
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• 1993

Kinetic studies are conducted for the reactions of Y-benzoyl, Y-benzenesulfonyl and Y-benzyl halides with X-anilines in acetonitrile, and the transition state (TS) structures and their variations with substituents X and Y are discussed. The magnitude of the cross-interaction constants, $\rho$xy, is the largest and the inverse secondary kinetic isotope effect (SKIE), $k_H/k_D$ < 1.0, with deuterated aniline nucleophiles is the smallest for benzoyl fluoride reflecting the tightest TS for this compound. The SKIEs for sulfonyl halides are relatively large due to a relatively large, diffuse nature of the reaction center, S, causing weaker steric hindrance to the vibrations of the two N-H(D) bonds. For benzoyl and sulfonyl halides, the trends in $k_H/k_D$ and $Ir_XI$ variations with $\sigma$Y contradict each other, which is rationalized by the negative charge accumulation on the reaction center, CO and SO$_2$, causing inefficient transfer for the substrate with an electron donating substituent.

• Journal of the Korean Chemical Society
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• v.20 no.3
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• pp.221-228
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• 1976

The kinetics of hydrolysis of hydrazonyl bromides $(p-H,\;p-CH_3,\;p-OCH_3,\;p-Br,\;p-Cl\;&\;p-NO_2)$ have been investigated by UV spectrometry in $60{\%}$ dioxane-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH2, the rate of hydrolysis of a series of hydrazonyl bromide is accelerated by electrondonating group (${\rho}$ = -0. 94) whereas at the pH values greater than 4, the ${\rho}$-value is 0.54. The rate equation, solvent-, substituent-and bromide ion-effect on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism: below pH 2, the hydrolysis proceed through $S_N2$, however, above pH 4, the hydrolysis is started by the attack of hydroxide ion and in the range pH 2{\sim}$4, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.150-157
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• 1978

The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

• Journal of the Korean Chemical Society
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• v.23 no.1
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• pp.37-41
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• 1979

The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$ and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with ${\sigma}$ substituent constant, especially using the new ${\sigma}$ value of 0.35 in p-MeO and it's ${\rho}$ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. $Br{\"{o}}nsted$ linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C${\cdot}{\cdot}{\cdot}$O bond in the $S_N2$ transition state proceed the bond formation.

• Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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• 2007.10a
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• pp.758-760
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• 2007

Organic field-effect transistors (OFETs) are of interest for use in widely area electronic applications. We fabricated a copper phthalocyanine (CuPc) based field-effect transistor with different metal electrode. So we need the effect of the substituent group attached to the phthalocyanine on the surface potential was investigated by Kelvin probe method with varying temperature of the substrate. We were obtained the positive shift of the surface potential for CuPc thin film. We observed the electron displacement at the interface between Au electrode and CuPc layer and we were confirmed by the surface potential measurement.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.352-358
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• 1987

Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

• Journal of the Korean Chemical Society
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• v.40 no.10
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• pp.663-669
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• 1996

The rate constants for the nucleophilic addition reactions of thioglycolic acid to vinylsulfilimine(VSI) derivatives(p-OCH3, H, p-Cl and p-Br) were determined by an ultraviolet spectrophotometric method, and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base catalysis and substituent effect, a plausible addition reaction mechanism was proposed: Below pH 3.0, the reaction was proceeded via the addition of neutral molecule to carbon-carbon double bond after protonation at the nitrogen atom of the sulfilimine, and in the pH range of 3.0 to 9.0, the neutral molecule and its anion attacked to carbon-carbon double bond competitively. Above pH 9.0, sulfide anion added to the double bond (Michael type addition).