• 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.

• 한국생물공학회:학술대회논문집
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• 2000.11a
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• pp.216-219
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• 2000

Pyrolysis products of woody biomass were consistedofvarious linear hydrocarbon, aromatics or condensed cyclic compounds. In order to obtain biomass pyrolysis products, more equipments and time were needed. But solvolysis of woody biomass with acetone easily obtained decomposition products and enhanced conversion rate(18.72%, max.) from woody biomass than pyrolysis of woody biomass. Beacause solvolysis with acetone improved conversion rate (26.64%, max.) of lignin. the whole conversion rate was improved. But above $300^{\circ}C$, lignin showed lower conversion rate, so the whole conversion rate decreased. Solvolysis products of woody biomass with acetone were same as pyrolysis products. Above $400^{\circ}C$, methoxy phenols were completely disappeared.

• Journal of the Korean Chemical Society
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• v.32 no.6
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• pp.581-587
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• 1988

The solvolysis of substituted benzyl bromides was studied in binary solvent mixtures of acetone-water and ethanol-water at $25^{\circ}C$ and $45^{\circ}C$. The rate constants increase with electron-donating substituents in benzene ring and increasing of water contents in both of solvent mixtures. The sensitivity parameter (m) of the solvolysis of substituted benzyl bromides to solvent ionizing power (Y) was decreased in going from the electron-donating group to electron-withdrawing one, whereas their nucleophilic sensitivity increased continuously in going to above same substituents. It was shown that electron-donating (electron-withdrawing) groups make the transition state looser (tighter). The above results were consisted with the account for the potential energy surface model and the quantum mechanical approach.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.1-7
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• 1980

Solvolysis rate constants for methylchloroformate, methylthionochloroformate, methylthiolchloroformate and methyldithiochloroformate have been determined conductometrically in methanol, ethanol and ethanol-water mixtures and activation parameters have been derived. Results show that methylchloroformate solvolyzes through $S_N2$ process while methyldithiochloroformate solvolyzes by $S_N1$ process in all the solvent systems. The rate of hydrolysis decreased in the order, $CH_3S(CS)Cl>CH_3S(CO)Cl>CH_3O(CS)Cl>CH_3O(CO)Cl$ which corresponds to the order of decreasing $S_N1$ character. In methanol, $CH_3S(CS)Cl$ solvolyzed via the $S_N1$ mechanism while the others solvolyzed via the $S_N2$ process. In ethanol, however, $S_N2$ character was dominant for all the compounds, except methyldithiochloroformate, for which $S_N1$ character was still strong enough to accelerate the rate of ethanolysis. In ethanol-water mixtures, $CH_3S(CS)Cl$ and $CH_3S(CS)Cl$ solvolyzed via $S_N2$ process in ethanol-rich region while the $S_N1$ character increased greatly in water-rich region for the solvolysis of these compounds. The order of $S_N1$ character for solvolysis in water-rich region was the same as the order of hydrolysis rate.

• Journal of the Korean Chemical Society
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• v.29 no.6
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• pp.629-636
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• 1985

The rates of solvolysis of trans-$[Co(AA)_2Cl_2]^+$ in which AA indicates ethylenediamine(en), N-ethylethylenediamine (N-eten), N-methylethylenediamino (N-meen) and trimethylenediamine(tn) respectively have been investigated using conductometric and spectrophotometric methods at various pressure up to 2,000 bar in acetone-water mixture. The activation volumes (${\Delta}V^{\neq}) obtained from the pressure effect on rate constants were -0.2∼0.9 $cm^3mole^{-1}$ for en, -0.2∼0.6 $cm^3mole^{-1}$ for N-eten, -0.8∼6.0 $cm^3mole^{-1}$ for N-meen and 0.7∼7.0$cm^3mole^{-1}$ for tn. The rates of solvolysis of these complexes were analyzed by comparing with the results obtained from excess free energy ($G^E$) and free energy cycle. It was found that $S_N1$ character was increased with decreasing the pressure and increasing the content of acetone in the mixture solvent. In addition to that, the effect of charge separation on the mechanism of solvolysis was discussed.

• Bulletin of the Korean Chemical Society
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• v.25 no.2
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• pp.307-310
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• 2004

• Bulletin of the Korean Chemical Society
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• v.29 no.11
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• pp.2145-2151
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• 2008

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3799-3801
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• 2011

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1729-1733
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• 2012

The solvolysis rate constants of 2,2,2-trichloroethyl chloroformate ($Cl_3CCH_2OCOCl$, $\mathbf{3}$) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $1.28{\pm}0.06$ and $0.46{\pm}0.03$ for $l$ and $m$, respectively. The activation enthalpies (${\Delta}H^{\neq}$) are 10.1 to 12.8 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) are -27.8 to -36.8 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect ($k_{MeOH}/k_{MeOD}$) of 2.39 is also in accord with $S_N2$ mechanism probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.31 no.7
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• pp.1963-1967
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• 2010

The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.