• Journal of the Korean Applied Science and Technology
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• v.14 no.3
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• pp.39-46
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• 1997

Ultraviolet spectrophotometric investigation has been carried out on the rate constants for 1,3-dipolar cycloaddition of 4-substituted-3-phenyloxadiazole derivatives with dipolarophiles such as phenyl acetylene, propiolic acid methyl ester and dimethylacetylene dicarboxylate. From there, the rate constants for 1,3-dipolar cycloaddition were determined at 80, 100 and $120^{\circ}C$, and the reaction rates were increased with increasing temperature. From these rate constants, the values of the thermodynamic activation parameters were obtained. Some thermodynamic activation parameters such as $E_{\alpha}$, ${\Delta}H^{\ast}$, ${\Delta}S^{\ast}$ and ${\Delta}G^{\ast}$ from Arrhenius equation were also calculated for the electrophilic 1,3-dipolar cycloaddition of 3-phenyloxadiazole derivatives with dipolarophiles. In order to the proposal the mechanism and reactivity of 1,3-dipolar cycloaddition reaction, the effect of substituents having various kinds of electron withdrawing or releasing groups were examinated. Considering the effect of substituents, an electron withdrawing group attached at the 4-carbon position in 3-phenyloxadiazole derivatives decreases the reaction rate because of the lack of electron density in 3-phenyloxadiazole ring.

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.209-214
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• 1990

A series of compounds consisting of 4'-oxybenzylidene-4-n-butylaniline, a mesogen, and a p-substituted phenoxyterephthaloyl structure a non-mesogen, interconnected through a central hexamethylene spacer were synthesized and their thermal behavior and liquid crystallinity were studied. p-Substituents included in this study are H, Cl, CN, $NO_2,\;n-C_4H_9O$ and phenyl groups. The compounds having phenyl and $n-C_4H_9O$ substituents are enantiotropic and form smectic-A(SA) and nematic (N) phases. The compound with $NO_2$ substituent is monotropic and forms only a nematic phase on heating the solid, whereas it forms nematic as well as $S_A$ phases on cooling the isotropic liquid. The rest compounds were found to be non-liquid crystalline. This is in great contrast to the fact that the monomesogenic model compound 4'-n-hexyloxybenzylidine-4-n-butylaniline forms $S_B,\;S_C,\;S_A$ and N phases enantiotropically.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

• Bulletin of the Korean Chemical Society
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• v.9 no.3
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• pp.167-171
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• 1988

Formation of intermolecular charge-transfer complexes between 7,7,8,8-tetracyanoquinodimethane (TCNQ) and two different series of stilbene derivatives has been studied spectroscopically at $25^{\circ}$C in 1,2-dichloroethane. The compounds of Series I include stilbene and derivatives which have fused phenyl rings on one end of the central ethylene structure and a phenyl ring on the other end. The other Series, II, is comprised of stilbenes which have various para substituents on one of the two phenyl rings. The equilibrium constant, $K_c^{AD}$ and the molar extinction coefficient, ${\varepsilon}_{\lambda}^{AD}$, were determined using the Scott equation. The values of the charge-transfer transition frequency, ${\vu}_AD$ and $K_c{AD}$ correlated well respectively with the ionization potentials of the fused rings of Series Ⅰ or of the compounds of Series II and with the values of ${\sigma}_p$, the Hammett constants of the Series II substituents. trans-4-N,N-Dimethylaminostilbene and trans-4-nitrostilbene were found to be able to participate in electron transfer reaction with TCNQ forming the corresponding anion radical, TCNQ$^-$:

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.168-170
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• 1987

The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

• The Korean Journal of Pesticide Science
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• v.5 no.3
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• pp.12-17
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• 2001

A new 2,3-dihydro-2,3,4,6,7-pentamethylbenzofuran-5-yl substituents in 5-benzofuryl-2-[1-(alkoxyimine) alkyl]-3-hydroxycyclohex-2-en-1-ones were found to have herbicidal activity against rice plant (Oryza sativa L.) and barnyard grass (Echinochloa crus-galli) under submerged conditions. The structure activity. relationships (SARs) on the herbicidal activity of $R_1\;and\;R_2$ on the azomethine bond of 2,3-dihydro-2,3,4,6,7-pentamethylbenzofuran-5-yl subsituents were analysized. The conditions of the selective herbicide activity between rice plant (seed) and barnyard grass from the basis on the analysized SARs are assumed that the $R_2$ group of ethyl substituent ($R_1$ ) should have optimal asymmetry parameter, $(L/B_1)_{opt.}=3.96{\AA}$. And also, the $R_2$ groups consist of $C_1{\sim}C_3$ and unsaturated group such as 3-chloro-2-propenyl group was contribution to the herbicide activity.

• Applied Biological Chemistry
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• v.40 no.1
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• pp.80-84
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• 1997

Series of new chiral N-substituted benzotriazol-1-yl derivatives were synthesized and their fungicidal activities in vitro against gray mold(Botrytis cinerea), black spot(Alternaria kikuchiana) and phytophthora blight(Phytophthora capsici) were measured by the agar medium dilution method. The substituents effects between the fungicidal activities (obs. $pI_{50}$) and a various physicochemical parameters of phenoxy or thiophenoxy group(X) & alkyl or phenyl group(Y) were analyzed by the multiple regression technique. From the analyzed substituent effects, the structure-activity relationship(SAR) equations shows that the antifungal activities depend on the parameters for the optimal molecular hydrophobicity($({\Sigma}logP)_{opt}$), Van der Waals (${\Sigma}Vw$>0) volume(${\AA}^3$) and inductive constant with electron withdrawing group(${\sigma}_I$,Y>0). The activity in affected by the inductive effect (${\sigma}_I$,Y>${\sigma}_g$X) of Y-group rather than the X-group. The phenoxy substituents, 1, showed higher antifungal activity tn the thiophenoxy substituents, 2. For 1, polar substituent constant(${\sigma}^*$) was an important factor in determining the activity. And the tribromomethyl substituent, 1g showed the highest activity against the tee fungi.

• Applied Biological Chemistry
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• v.50 no.3
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• pp.147-153
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• 2007

To search for a molecular design of a new breast cancerous inhibitory active compound, 2D-QSAR and HQSAR between the substituents of flavopiridol analogues as substrates and their breast cancerous inhibitory activities against MCF-7 cell were analyzed and discussed quantitatively. It was found that the dispersion with molecule and steric hindrance with substituents will have a tremendous impact on the inhibitory activities from the 2D-QSAR model (1). Also, MR constant is better than that of MS constant as animportant factor. The inhibitory activities from 2D-QSAR model (2) were dependent upon the optimum MR constant (MR = 126 $Cm^3/mol$). Optimized HQSAR model (V) exhibited the best predictability of the inhibitory activities based on the cross-validated $r^2_{cv}$($q^2$= 0.583) and non-cross-validated conventional coefficient ($r^2_{ncv}$= 0.982). From the contribution maps, the inhibitory activity by the imino group on $C_9$ atom was higher than that of the hydroxyl group of $C_8$ atom on the A ring in molecule. Therefore, we can confirm that the dispersion by substituents in molecule is the most important factor in inhibitory activities against MCF-7 cell.

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.28-42
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• 1999

Polysilanes with sterically bulky substituents, -[2-( $R^1R^2$-phenyl)propyl]Si[$R^3$]-, such as poly(2-phenylpropyl)(n-hexyl)silane [$R^1=R^2$=H, $R^3$=n-hexyl] were prepared by Wurtz-type coupling reactions with Na using a sonochemical method. The high-intensity ultrasound provided the formation of high quality Na dispersion in toluene and its active surface which was important for the synthesis of polysilanes in Wurtz-type coupling reaction was freshly and continuously regenerated during the process. The polysilanes products were mixtures of high molecular weight polymers with $\={M}_W$ of ∼$10^6$ and low molecular weight polymers with $\={M}_W$ of ∼$10^3$. It was found that the formation of high molecular weight polymerr was greatly influenced by the substituents $R^3$, directly attached to Si. On the contrary, changes on substituents ($R^1, R^2$) gave no influences at all. Overall yields for polysilanes were 75-99% in general but high molecular weight polysilanes were obtained as a major product when substituent $R^3$ is n-hexyl group and low molecular weight polysilanes were obtained as a major product when substituent $R^3$ is cyclohexyl and 2-phenylethyl groups. Effects of reaction conditions to polysilane yields were investigated.

• Applied Biological Chemistry
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• v.38 no.4
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• pp.359-363
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• 1995

New ten N-[1-(benzotriazol-1-yl)alkyl]aniline(4) derivatives were synthesized and the crystal structure of 4h was shown by X-ray crystallography and the absolute configuration has been assigned as S form. The molecule crystallizes in the monoclinic system, space group $P2_{1}/n$. And the molecules in the crystal are linked with each other through the hydrogen bond $(N_{11}-H_{11}{\cdots}N3)$ with distance $2.300(11){\AA}$ The fungicidal activity($pI_{50}$) in-vitro against Botrytis cineria (BC), Phytophthora casici (PC) and Sclerotium cepinorum (SC) were determined by the agar dilution method. The structure activity ralationships (SAR) between structure of 4 and the activity were studied using a physicochemical parameters of substituents and multiple regression technique. Among these compounds, only the bromo group substituent(4f) showed higher activity, which depend on the hydrophobic(${\pi}$) of substituents. The relative orders of the activity are SC>BC> and PC, respectively. This implies that the activity is affected by the hydrophobic(${\pi}$) nature of the Z group rather than the X group. Linear free energy relationships(LFER) on the fungicidal activity with substituents has been also discussed.