• Journal of the Korean Chemical Society
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• v.65 no.5
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• pp.309-312
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• 2021

The solvolysis of (1s)-(+)-menthyl chloroformate (1) were studied kinetically in 28 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolysis of 1 obtained the l value of 2.46 ± 0.18, the m value of 0.91 ± 0.07, and the correlation coefficient of 0.950. The solvolysis of 1 might proceed via an associative S_N2 mechanism enhancing bond making than bond breaking in the transition state (TS). The value of l/m is 2.7 within the ranges of value found in associative S_N2 reaction. This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.16).

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1451-1456
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• 1999

Solvolyses of α-methoxy-α-(trifluoromethyl)phenylacetyl chloride in H₂O, D₂O, CH₃OD, 50% D₂O-CH₃OD, and in aqueous binary mixtures of acetone, dioxane, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of first-order rate constants for α-methoxy- α-(trifluoromethyl)phenylacetyl chloride with $Y_{Cl}$ show a dispersion phenomenon. Solvent nucleophilicity N has been shown to give considerable im-provement when it is added as an 1N term to the original Grunwald-Winstein for the solvolyses of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by solvent nucleophilicity. The magnitude of l and m values associated with a change of solvent composition predicts the associative $S_N2$ transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed associative $S_N2$ or $S_AN$ mechanism for the of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride.

• Journal of the Korean Chemical Society
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• v.62 no.4
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• pp.265-268
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• 2018

The solvolyses of anthraquinone-2-carbonyl chloride (1) were studied kinetically in 27 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolyses of anthraquinone-2-carbonyl chloride (1) obtained the l value of $2.11{\pm}0.11$, the m value of $0.54{\pm}0.06$, and the correlation coefficient of 0.955. The solvolysis reaction of 1 might proceed via an associative $S_N2$ mechanism enhancing bond making than bond breaking in the transition state (TS). This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.27).

• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.85-91
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• 1999

The second order rate constants for the hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates (2,4-$(NO_2)_2$, 4-$NO_2$, 4-CN, 4-Cl, 4-H)in 20% dioxane-water (v/v) have been determined by UV/Vis spectrophotometric method at various temperatures. The activation parameters (Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$) were calculated from the rate constants and the reaction constant ($\rho$) was also estimated by Hammett equation. The activation entropies of the title reactions show considerably negative values, this result is not consistent with a dissociative mechanism (EA) in which a positive or a slightly negative value of the entropy of activation should be expected. Further, kinetic evidence for an associative mechanism (AE) was obtained from the linear free energy relationship. By the results of kinetic study for the alkaline hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates, it may be concluded that these reactions proceed through an associative mechanism.

• Journal of the Korean Chemical Society
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• v.22 no.5
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• pp.281-288
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• 1978

Pseudo-first order rate constants $k_{obs}$ were determined for the reactions of naphthalenesulfonyl chlorides (1-NSC and 2-NSC) and anilines. The second order rate constant $k_2$ and third order catalytic $k_3$ were then determined from $k_{obs}$. For 1-NSC peri-hydrogen effect was observed. The large Brønsted ${\beta}$ and large negative slopes ${\rho}$ for the Hammett plots were obtained. These results with the unsually low values of activation parameters were consistent with the $S_AN$-elimination mechanism, but these can be equally well interpreted with the associative $S_N2$mechanism.

• Journal of the Korean Chemical Society
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• v.43 no.5
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• pp.505-510
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• 1999

$TiO_2$ powders were prepared via hydrolysis of titanium n-butoxide in n-butanol and hydrolysis mechanism of titanium n-butoxide was studied using UV-Vis spectrometer. Hydrolysis reactions were controlled to proceed to pseudo-first order reaction in the presence of excess water. The phases of $TiO_2$ powders, prepared under the these conditions, were identified by XRD and reaction rates were calculated by Gugggenheim method. Prepared powders were noncrystalline states in their initial stage of formation but transformed to crystalline rutile structure by heating. Reaction mechanism of titanium n-butoxide was proposed as Interchange-Associative(Ia) mechanism, based on the data of n-value and termodynamic parameters which were determined from the rate constants.

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.47-50
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• 1989

The methanolysis reactions of phenylacetyl chlorides have been investigated in methanol-acetonitrile mixtures at temperatures ranging - $15.0-0.0^{\circ}C.$ Substituent and solvent effects on the rate supported an associative $S_N2$ mechanism for the solvolysis. Activation parameters indicated that the reaction is entropy controlled, while the a/s ratios of the Taft's solvactochromic correlation proved to be remarkably constant with a typical value of 0.50 that is consistent for the reactions proceeding by a typical $S_N2$ path.

• Bulletin of the Korean Chemical Society
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• v.2 no.2
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• pp.41-45
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• 1981

For solvolyses of benzenesulfonylchlorides we determined transfer enthalpies of transition states, and solvent (TFE + EtOH) and substituent effects on rates. We have used the More O'Ferrall plots to show that transition states variation caused by solvent and substituent changes is consistent with an associative $S_N2$ mechanism for the nucleophilic substitution reaction of benzenesulfonylchlorides.

• Bulletin of the Korean Chemical Society
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• v.6 no.2
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• pp.99-102
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• 1985

Substituent effects of substrate and nucleophile for the reaction of substituted phenacyl tosylates with pyridines were determined conductometrically in acetonitrile. Activation parameters for these reactions were also calculated. The substituent effects in nucleophile were increased with electron-donating power of pyridines and Br${\o}$nsted linear relationship was shown. Rate constant was increased by both electron-donating and electron-attracting groups in the substrate. It seems that dissociative S$_{N}$2 ("loose" transition state) mechanism is operating in the case of electron-donating substituents while associative S$_{N}$2 ("tight" transition state) mechanism is operative in the case of electron-attracting substituents.

• Applied Chemistry for Engineering
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• v.8 no.5
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• pp.777-783
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• 1997

$TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.