• Proceedings of the PSK Conference
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• 2002.10a
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• pp.395.1-395.1
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• 2002

Many of the chiral NSAIDs are marketed as racemates. There is an increasing interest in developing the enantiomerically pure forms of the NSAIDs because the anti-inflammatory activity of NSAIDs have previously been shown to be largely sterospecific for the (S)-(＋)-enantiomer. Therefore, simple and economic preparative method to identify the (S)-(＋)-enantiomer of NSAIDs (aryl propionic acids) as diastereomeric solvation complex was developed using several chiral solvating agents by recrystallization of racemate and solvent fractionation. (omitted)

• Journal of the Korean Chemical Society
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• v.23 no.6
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• pp.339-348
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• 1979

The kinetics of the solvolysis of 2-furoyl chloride and 2-thenoyl chloride in $MeOH-H_2O,\;EtOH-H_2O,\;(Me)_2CO-H_2O,\;MeCN-H_2O$ and MeCN-MeOH has been investigated. The rates were faster in protic solvents than in aprotic solvents. This was caused by the bond breaking of leaving group through hydrogen-bonding solvation of protic solvents. In MeCN-M$\'{e}$OH the rate in MeOH rich solvents was faster than in MeCN rich solvents by the specific solvation of alcoholic hydrogen and there was a maximum rate of reaction at MeOH mole fraction of 0.8. The reaction rates of solvolysis were considerably slower than those of benzoyl chloride owing to the electron withdrawing effect of thienyl and furyl groups. It was concluded that solvolytic reaction proceeds via a dissociative $S_N2$ mechanism in which bond-breaking precedes bond-formation at the transition state.

• Journal of the Korean Chemical Society
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• v.24 no.4
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• pp.288-294
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• 1980

Methanolysis rate constants were determined for $CH_3O(CO)Cl,\;CH_3S(CO)Cl\;and\;CH_3S(CS)Cl\;in\;CH_3OH-CH_3CN$ mixtures. Results show that the rates are not predominantly influenced by the bulk solvent properties but are partly influenced by specific electrophilic solvation.Polarity of the solvent is not a dominant factor but it nevertheless plays a role in charge stabilization of the $S_N1$ like transition state. The methanolysis proceeds through $S_N1$ mechanism for $CH_3S(CS)Cl$ for which both specific solvation of leaving group by methanol and charge stabilization by a high dielectric medium are important, while for $CH_3O(CO)Cl\;methanolysis occurs\;via\;S_N2$ mechanism in which both of the solvent effects are unimportant.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.419-424
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• 1987

Kinetic studies on the solvolysis of para-methyl benzyl nitrate and benzyl nitrate were carried out in aqueous methanol, ethanol, acetonitrile, acetone, tetrahydrofuran and dioxane mixtures at 60$^{\circ}$C. The rates were faster in protic solvent mixtures than in aprotic solvent mixtures. This was considered in the light of transition state stabilization by hydrogen bonding solvation of protic solvent mixtures. Grunwald-Winstein equation, extended Grunwald-Winstein equation and correlation between E$_T$(30) and rate constant were applied in order to discuss the transition state variations caused by changing benzyl substituents and solvents. The results showed that strong electrophilic assistance of solvent is operative in the the water-rich solvents.

• Applied Chemistry for Engineering
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• v.20 no.6
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• pp.685-691
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• 2009

Dispersions of fumed silica are made in 6 kinds of mono-solvents and mixed solvents which have hydroxyl group, non hydroxyl group, different polarity, and different molecular size. The viscosity and rheology behaviors of the each dispersion are investigated according to the viewpoint of solvent characteristic. The silica dispersion in polar solvent with hydroxyl group is stable and low viscous sol. The silica dispersion in non-polar solvent with non-hydroxyl group is high viscous gel. When the solvent with hydroxyl group is added to the silica dispersions with non-polar solvents, they show the reduction of viscosity with solvent content. They have minimum critical content which shows no viscosity change. The minimum critical solvent content is decreased according to the polarity of solvents with no hydroxyl group. The solvation layer which is formed on the silica surface through hydrogen bonding between hydroxyl-containing solvent and the silanol group of silica surface is the reason of stable and low viscous sol. In case of non-polar solvent, silanol on adjacent silica particles interacted directly by hydrogen bonding show high viscous and flocculated gel.

• Journal of the Korean Chemical Society
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• v.38 no.3
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• pp.221-223
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• 1994

We tried to apply the linear solvation energy comparison method to solute retention in normal phase liquid chromatography. Correlation coefficients of regression of lnk' collected in a fixed eluent against solute polarity indices have proven to be lower than those obtained from reversed phase liquid chromatography data. This event can be attributed to complexity of solute retention process in normal phase liquid chromatography. We concluded from the regression results that each specific polarity of the stationary phase is greater than that of the mobile phase and that the difference in each polarity between the stationary phase and the mobile phase decreases as the volume fraction(${\phi}$) of the more polar solvent in the mobile phase increases. Correlations of lnk' of a single solute against solvent polarity indices have proven to be meaningless owing to covariance among the solvent polarity indices. Instead, a good linear relationship between lnk' and solvent ${\pi}^*$ was observed, and its linearity is better than that between lnk' and ${\phi}$.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.3-9
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• 1993

Specific rates of solvolysis of 1-adamantyl fluoroformate in hydroxylic solvents have been measured by an electric conductivity method under various pressures. The activation parameters (${\Delta}V^{\neq}{_o},\;{\Delta}{\beta}^{\neq},\;{Delta}H^{\neq},\;{Delta}S^{\neq}$,/TEX>) and average pressure within the solvation-shell of activated complex (charge development) have been estimated from the rates. Also, the selectivities for the formation of solvolysis products in aqueous ethanol have been determined by response-calibrated GC. The values of ${\Delta}V^{\neq}{_o},\;and\;{\Delta}{\beta}^{\neq}$ are both negative, but ${Delta}H^{\neq}$ is positive and ${Delta}S^{\neq}$, is large negative. This behavior is discussed in terms of electrostriction of solvation. From these results, it could be postulated that the solvolysis of 1-adamantyl fluoroformate have two major reaction pathway.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2251-2255
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• 2013

Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.905-908
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• 2000

Second-order rate constants have been measured spectrophotometrically for the hydrolysis of p-nitrophenyl ac-etate (PNPA) and p-nitrophenyl diphenylphosphinate (PNPDPP) with MO42- (M = Cr, Mo and W) in phos-phate buffer (pH = 8.00) at 35.0 $^{\circ}C.$ Thes e MO42- species exhibit large catalytic effect in the hydrolysis of PNPA and PNPDPP except WO42- in the reaction with PNPA. The catalytic effect of these MO42- species has been observed to be much more significantin the hydrolysis of PNPDPP than in the hydrolysis of PNPA. Since the smallest CrO42-would be most highly solvated by H2O molecules, CrO42- is expected to exhibit the least catalytic effect, if solvation effect is the most important factor. However, in fact, CrO42- shows the highest cat-alytic effect toward PNPA, indicating that solvation effect is not solely responsible for the catalytic effect. The most basic CrO42- shows the highest catalytic effect, while the least basic WO42- is least reactive toward PNPA, indicating that the basicity of MO4 2- might bean important factor. However, in the hydrolysis of PNPDPP, no correlation is observed between the basicity and catalytic effect, suggesting thatbasicity alone can not be re-sponsible for the catalytic effect shown by the MO42- species. Formation of a chelate is suggested to be respon-sible for the high catalytic effect of MO42- in the hydrolysis reaction of PNPA and PNPDPP. The formation of chelate is considered to be more suitable for the reaction with PNPDPP than with PNPA based on the larger catalytic effect observed in the reaction with PNPDPP than with PNPA.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2711-2718
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• 2012

The alkylation of the ambident enolates of a methyl glycinate Schiff base with ethyl chloride was studied at B3LYP and MP2 levels with $6-31+G^*$ basis set. The free (E)-enolates and (Z)-enolate are similar in energy and geometry. The transition states for the alkylation of the free (E)/(Z)-enolate with ethyl chloride have similar energy barriers of ~13 kcal/mol. However, with a lithium ion, the (E)-enolate behaves as an ambident enolate and makes a cyclic lithium-complex in bidentate pattern which is more stable by 11-23 kcal/mol than the (Z)-enolate-lithium complexes. And the TS for the alkylation of (E)-enolate-lithium complex coordinated with one methyl ether is lower in energy than those from (Z)-enolate-lithium complexes by 4.3-7.3 kcal/mol. Further solvation model (SCRF-CPCM) and reaction coordinate (IRC) were studied. This theoretical study suggests that the alkylation of ambident enolates proceeds with stable cyclic bidentate complexes in the presence of metal ion and solvent.