• Archives of Pharmacal Research
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• 제19권6호
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• pp.543-550
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• 1996

Analogues of $2(S)-5, 2^{l}, 5^{l}$-trihydroxy-7, 8-dimethoxyflavanone, a naturally-occurring compound, which had been reported to have potent antitumor activity, were synthesized and examined for the cytotoxicity against three cancer cell lines. Among the intermediate chalcones and synthetic 5-hydroxy-7, 8-dimethoxyflavanone analogues, $({\pm})2^{l}, 5^{l}-dibenzyloxy-5, 7, 8-trimethoxyflavanone$ exhibited about 2-8 times stronger activity than $2(S)-5, 2^{l}, 5^{l}$-trihydroxy-7, 8-dimethoxyflavanone against L1210, K562 and A549 cancer cell lines. In the structure-activity relationship, it is suggested that among analogues of 5-hydroxy-7, 8-dimethoxyflavanone, the existence of two oxygenated groups of para-relation at $C-2^{I} and C-5^{I}$ positions on flavanone B-ring, may be necessary to exhibit effective cytotoxic activity.

• Bulletin of the Korean Chemical Society
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• 제14권1호
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• pp.43-47
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• 1993

Poly(2-cyano-5-methoxy-1,4-phenylenevinylene), PCMPV and a series of PPV copolymers containing 2-cyano-5-methoxy-1,4-phenylenevinylene (CMPV) units were prepared via the water-soluble precursor method. They were obtained in films form and were easily doped with $FeCl_3$. Doping of undrawn and drawn films of PCMPV homopolymer with $FeCl_3$ led to conductivity of $10^{-5}-10^{-4}\;Scm^{-1}$. Conductivity of $FeCl_3$-doped copolymer films ranged from $10^{-3}$ 4.0 Scm$^{-1}$ depending on composition. As the content of CMPV units in the copolymer increased further, the electrical conductivity steadly decreased. Electronic effect by the CN substituent and morphological changes brought by copolymerization appear to interplay intricately resulting in the observation of a maximum conducting composition.

• Bulletin of the Korean Chemical Society
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• 제20권6호
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• pp.712-714
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• 1999

The rate constants for the nucleophilic addition of potassium cyanide to α,N-diphenylnitrone and its derivatives (p-OCH3, p-CH3, p-Cl, and p-NO2) were determined by ultraviolet spectrophotometer at 25℃, and the rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: At high pH, the cyanide ion to carbon-nitrogen double bond was rate controlling, however, in acidic media, the reaction proceeded by the addition of hydrogen cyanide molecule to carbon-nitrogen double bond after protonation at oxygen of a,N-diphenylnitrone. In the range of neutral pH, these two reactions occured competitively.

• Bulletin of the Korean Chemical Society
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• 제18권8호
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• pp.880-886
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• 1997

Ab initio calculations were carried out on the gas phase acid-catalyzed hydrolysis reactions of sulfinamide using the 3-21G* basis sets. Single point calculations were also performed at the MP2/6-31G* level. The first step in the acid-catalyzed hydrolysis of N-methylmethanesulfinamide, Ⅰ, involves protonation. The most favorable form is the O-protonated one, Ⅱ, which is then transformed into a sulfurane intermediate, Ⅲ, by addition of a water molecule. The reaction proceeds further by an intramolecular proton transfer from O to N (TS2), which is followed by N-S bond cleavage (TS3) leading to the final products. The rate determining step is the N-S bond cleavage (TS3) at the RHF/3-21G* level, whereas it becomes indeterminable at the MP2/6-31G*//3-21G* level of theory. However, the substituent effect studies with N-protonated N-arylmethanesulfinamide, ⅩⅢ, at the MP2/6-31G*//3-21G* level support the N-S bond breaking step as rate limiting.

• Bulletin of the Korean Chemical Society
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• 제18권4호
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• pp.374-379
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• 1997

The rate constants for the nucleophilic addition of thiophenol derivatives (p-OCH3, H, p-CH3, m-CH3, p-Br and p-NO2) to 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide (AMQD) were determined by ultraviolet spectrophotometer in water at 5 ℃, and rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, Bronsted plot, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: Below pH 2.5, the reaction proceeded by the addition of thiophenol molecule to 6'-position of quinonoid after protonation at the acridinyl nitrogen. Above pH 6.2, the addition of sulfide anion to 6'-position of quinonoid was rate controlling. However, in the range of pH 3.0-6.0, these two reactions occured competively.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.573-576
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• 1999

The rate constants and kinetic solvent isotope effects (KSIE, KMeOH/kMeOD) for solvolyses of para-substituted phenylchloroformates in CH3OH, CH3OD, H2O, D2O, 50% D2O-CH3OD were determined at 15.0 and 25.0℃ using conductometric method. Kinetic solvent isotope effects for the solvolyses of para-substituted phenyl chloroformates were 2.39-2.51, 2.21-2.28, and 1.67-1.69 for methanol, 50% aqueous methanol, and water, respectively. The slopes of Hammett plot for solvolysis of para-substituted phenyl chloroformates in methanol, 50% aqueous methanol, and water were 1.49, 1.17 and 0.89, respectively. The Hammett type plot of KSIE, log (KSIE) versus p, can be a useful mechanistic tool for solvolytic reactions. The slopes of such straight lines for para-substituted phenyl chloroformates are almost zero in methanol, 50% aqueous methanol, and water. It was shown that the reaction proceeds via an associative SN2 and/or general base catalysis addition-elimination (SAN) mechanism based on activation parameters, Hammett p values, and slopes of Hammett type plot of KS-IE.

• Bulletin of the Korean Chemical Society
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• 제19권2호
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• pp.243-249
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• 1998

The reaction of alcohol with a solution of thexylborane (ThxBH2) in tetrahydrofuran (THF) provides a new class of mild and selective reducing agents, thexylalkoxyboranes (ThxBHOR: R=Et, i-Pr, i-Bu, s-Bu, t-Bu, Ph). In order to elucidate the effect of the alkoxy group in reduction reactions, the reducing power of ThxBHOR toward selected organic compounds containing representative functional groups under practical conditions (THF, 25°, the quantitative amount of reagent to compound) has been investigated. Generally, the reactivity of ThxBHOR is largely dependent upon the alkoxy substituent. ThxBHOR can be synthesized from a variety of alcohols, thus allowing control of the steric and electronic environment of these reagents.

• Bulletin of the Korean Chemical Society
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• 제13권3호
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• pp.259-265
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• 1992

Cyclic voltammetric behavior of symmetric (dimethyl, diheptyl, dioctyl, dibenzyl) and asymmetric (methyloctyl, methyldodecyl, methylbenzyl) viologens was investigated in homogeneous aqueous solution and sodium dodecyl sulfate (SDS) micellar media. In SDS-free 0.1 M NaCl solutions, the reduction potential is less negative as the chain length of alkyl substituent is longer. This is due to the stabilization of the reduced cationic radical and neutral form of viologen by adsorption on electrode surface. The adsorbed species show the "aging-effect". With the exceptions of methyldodecyl viologen and methylbenzyl viologen, the viologens show strong tendency of conproportionation reaction between viologen dications and neutral forms. In cases of methyldodecyl viologen and methylbenzyl viologen, the conproportionation reaction is kinetically disfavored, though it is thermodynamically favorable. SDS micelles dissolve the adsorbed species and the viologens exhibit two reversible redox processes in SDS micellar solutions. The reduction potentials of viologens in SDS micellar solutions depend little on the length of alkyl chain. Benzyl-substituted viologens are more easily reduced than the alkyl substituted viologens, presumably due to electron-withdrawing character of benzyl group.

• Bulletin of the Korean Chemical Society
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• 제12권3호
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• pp.301-303
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• 1991

The rate constants for the nucleophilic addition of thiophenol to $\alpha$, N-diphenylnitrone and it's derivatives (p-$OCH_3$, p-Cl, p-$NO_2$) were determined from pH 3.0 to 13.0 by UV spectrophotometry and rate equations which can be applied over a wide pH range were obtained. On the basis of rate equation, general base and substituent effect a plausible addition mechanism of thiophenol to ${\alpha}$, N-diphenylnitrone was proposed: At high pH, the addition of sulfide ion to carbon-nitrogen double bond was rate controlling, however, in acidic solution, reaction was proceeded by the addition of thiophenol molecule to carbon-nitrogen double bond after protonation at oxygen of ${\alpha}$, N-diphenylnitrone.

• Bulletin of the Korean Chemical Society
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• 제34권1호
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• pp.49-53
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• 2013

Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.