• Journal of the Korean Chemical Society
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• v.18 no.1
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• pp.8-11
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• 1974

The solvolysis of p-substituted benzenesulfonyl chlorides $(substituents:p-H, p-Br, p-NO_2, p-OCH_3)$ in acetonitrile-water mixtures below 50 % of water content has been studied kinetically. Results show that Hammett plots give concaved curves but the mechanism is predominantly $S_N2$ and water acts both as nucleophile and general-base.

• Bulletin of the Korean Chemical Society
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• v.2 no.3
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• pp.105-112
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• 1981

Various $3{\alpha}$, $5{\alpha}$-cyclocholestan-6${\beta}-yl$ ethers were synthesized from solvolysis reactions of cholesteryl tosylate. ${3\alpha}$, $5{\alpha}$-Cyclocholestan-6${\beta}-yl$ sulfides were the sole products when cholesteryl tosylate was solvolyzed in thiol solvents. Diol solvolysis products were derivatized to aromatic esters, and nuclear magnetic resonance spectroscopic method was used to show that aromatic rings can approach C-18 methyl group and the side chain.

• Bulletin of the Korean Chemical Society
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• v.3 no.1
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• pp.34-36
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• 1982

N-Methacryloyl-L-histidine and N-methacryloyl-L-histidine methyl ester were synthesized and polymerized to obtain polymeric catalysts with different functions. In the presence of each of these polymers the solvolytic reactions of p-nitrophenyl acetate (PNPA), 3-nitro-4-acetoxybenzoic acid(NABA), 3-acetoxy-N-trimethylanilinium iodide(ANTI) and 3-nitro-4-decanoyloxybenzoic acid(NDBA) were performed in 20% aqueous ethanol. For the purpose of comparison the low molecular weight analogs(LMWA's), L-histidine, L-histidine methyl ester and N-acetyl-L-histidine were also subjected to catalyze the solvolyses of above substrates. In the solvolysis of PNPA the polymeric catalysts exhibited lower activities than the LMWA's. However the ionic substrates, NABA and ANTI were solvolyzed at anomalous rate by polymeric catalyst, indicating that electrostatic effects are operative in the catalysis by polymers. Furthermore in the solvolysis of hydrophobic monomer NDBA, polymeric catalysts exhibited highly enhanced activities compared with the LMWA's implying that hydrophobic interaction can be the most important contribution to the high catalytic activity of imidazole-containing polymers.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1104-1108
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• 1995

A measure of stabilities (-ΔHo) and resonance delocalization (-Δq(Cα+)) for some carbocations has been estimated using the semiempirical AM1 method. The stability (-ΔHo) of carbocations can be correlated with the sensitivity (m) of localized cations to the solvent ionizing power scale Y, whereas the extent of resonance delocalization (-Δq(Cα+)) can be correlated with the sensitivity (h) of delocalized cations to the solvent ionizing power scale Ⅰ. It has been shown that two solvent ionizing power scales Y and I have in general opposite signs so that effects of electrostatic solvation are opposite for the localized and delocalized cationic charges. The use of two different solvent scales for a substrate with delocalizable cationic charge is not only prerequisite to the proper correlation of solvolysis rates but also is justified.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.636-642
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• 1992

Preferential solvation (PS) phenomena of solutes based on solvent polarity, $E_T$ and AN, were studied by UV/vis. and NMR spectra in MeOH binary mixtures. According to the extent of solvent-solvent interaction, different solvation phenomena were found. PS concept was applied to explain the reactivity of tert-butyl halides solvolysis. The findings of solvation phenomena have been related to the rate of solvolysis and PS suggested as a reason for the solvent dependence of the rates of reaction. Moreover, we found that the results of principal components analysis using six parameters are in good accordance with the results of PS phenomena in mixed methanol systems.

• Bulletin of the Korean Chemical Society
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• v.6 no.5
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• pp.259-263
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• 1985

Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and $40^{\circ}C$ under various pressures up to 1600 bar. The rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${\Delta}V^{\neq},{\Delta}{\beta}^{\neq},{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${\Delta}V^{\neq}\;and\;{\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation (electrostriction). From the relation between the reaction rate and the dielectric constant of solvent or the number of water molecule participated in the transition state, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

• Bulletin of the Korean Chemical Society
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• v.23 no.11
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• pp.1680-1682
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• 2002

• Bulletin of the Korean Chemical Society
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• v.22 no.11
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• pp.1264-1266
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• 2001

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3293-3297
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• 2012

The solvolysis rate constants of 5-nitro-2-furoyl chloride (5-$NO_2(C_4H_2O)$-2-COCl, 1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of $1.20{\pm}0.05$ and $0.37{\pm}0.02$ for l and m, respectively. The activation enthalpies (${\Delta}H^{\neq}$) were 5.63 to $13.0kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -25.9 to $-43.4cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.65 was also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The product selectivity (S) for solvolysis of 1 in alcohol/water mixtures was 1.2 to 11, which is also consistent with the proposed bimolecular reaction mechanism.

• Journal of the Korean Chemical Society
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• v.29 no.5
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• pp.465-471
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• 1985

The rate constants for the solvolysis of anthraquinone-2-carbonyl chloride in binary solvent mixtures, methanol-acetonitrile, methanol-acetone, ethanol-acetonitrile and ethanol-acetone, have been studied by means of conductometry. Maximum rate phenomena were observed at the methanol mole fraction, $X_{MeOH}$ = 0.73~0.81 for methanol-acetonitrile and at $X_{MeOH}$ = 0.83 for methanol-acetone mixtures. The Kivinen and Grunwald-Winstein plots indicated that the reaction proceeds via $S_N2$ type mechanism. Application of Taft's solvatochromic correlation on the solvolysis rate revealed that both $\alpha$ and ${\pi}^*$ are important for reactions in methanol-acetonitrile and methanol-acetone mixtures, while only ${\alpha}$ influences significantly on the rate in ethanol-acetonitrile and ethanol-acetone mixtures.