• Journal of the Korean Chemical Society
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• v.7 no.4
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• pp.264-270
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• 1963

The general equation for the substituent effect test, which was derived in the previous paper, has been extended to correlate thermodynamic parameters of solvolysis reaction by modifying the potential energy term to represent the effect of changes in solvent composition. The linear fits of the new equation, $\Delta{\Delta}H^\neq=a'Y+b\Delta{\Delta}S^\neq$, were tested with 35 examples from literature and average correlation coefficient of 0.977 was obtained. Examination of results showed that the equation is generally applicable to solvolysis reaction and helps elucidate some the difficulties experienced with the Grunwald-Winsteln equation. It has been stressed that the linear enthalpy-entropy effect exists only between the external enthalpy and entropy of activation, and therefore strictly it is the linear external enthalpy-entropy effect.

• 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.28 no.4
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• pp.259-264
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• 1984

The rate constants for the hydrolysis of benzenesulfonylimido phosgene at various pH were determined by ultraviolet spectrophotometry in 1 : 4 dioxane-water mixed solvents at 25$^{\circ}$C and a rate equation which can be applied over a wide pH range was obtained. Based on the Grunwald-Winstein equation, m = 0.4 was obtained. The thermodynamic activation parameters for the hydrolysis were ${\Delta}H^{\neq}$ = 15kcal mol$^{-1}$, ${\Delta}S^{\neq}$ = 21e.u. at pH 4.0 and $ {\Delta}H^{\neq}$ = 8kcal. mol$^{-1}$, ${\Delta}S^{\neq}$ = -39e.u. at pH 11.0, respectively. It was concluded that the hydrolysis of benzenesulfonylimido phosgene in 1 : 4 dioxane-water mixed solvents proceed via nucleophilic addition-elimination.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2413-2418
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• 2009

Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-N$O_2$PhOP(S)(Cl)OPh, $\underline{1}$) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate (($PhO)_2$PSCl, $\underline{2}$), diphenyl phosphorochloridate (($PhO)_2$POCl, $\underline{3}$), diphenyl phosphinic chloride ($Ph_2$POCl, $\underline{4}$), and diphenyl thiophosphinic chloride ($Ph_2$PSCl, $\underline{5}$). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate ($\underline{1}$) is suggested to be proceeded a $S_N$2 process as previously reported result. The activation enthalpies are shown as slightly low as ${\Delta}H^{\neq}\;=\;9.62\;to\;11.9\;kcal{\cdot}mol^{-1}$ and the activation entropies are shown as slightly high negative value as ${\Delta}S^{\neq}\;=\;-34.1\;to\;-44.9\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$ compared to the expected $S_N$2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical $S_N$2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in $H_2O/D_2O$ solvent mixtures.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.51-56
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• 2014

The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $0.93{\pm}0.14$ and $0.65{\pm}0.06$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.4 to $14.6kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -15.5 to -$32.3kcal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, $k_{ww}$ and $k_{aa}$, were calculated from the rate constants ($k_{obs}$), together with $k_{aw}$ and $k_{wa}$ calculated from the intercept and slope of the plot of 1/S vs. [water]/[alcohol]. The calculated rate constants, $k_{calc}$ ($k_{ww}$, $k_{aw}$, $k_{wa}$ and $k_{aa}$), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.123-129
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• 1990

The rate constants for the solvolysis of $trans-[Cr(en)_2Br_2]^+$ ion were determined by the spectrophotometric method in methanol-, ethanol-, acetone-, and acetonitrile-water mixtures, at 20, 25, 30, and 35$^{\circ}C$, respectively. The rate constants increased with increasing co-solvent compositions. The rate constant did not show any relation with the reciprocal of dielectric constant of the solvent-mixtures. The m values of Grunwald-Winstein equation for methanol-, ethanol-, acetonitrile-, and acetone-water mixtures are 0.109, 0.103, 0.101, and 0.095, respectively. A free energy cycle for the process from the initial state to the transition state in water and water + co-solvent mixtures shows that the change in solvation at the transition state has a dominant effect on the rate. From the above results, it is believed that the mechanism for the aquation of this complex is the Id mechanism.

• Journal of the Korean Chemical Society
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• v.37 no.8
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• pp.695-701
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• 1993

Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

• Journal of the Korean Chemical Society
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• v.31 no.1
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• pp.25-30
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• 1987

Solvolysis of tert-butyl halides and 1-adamantyl tosylate in methanol-acetone mixtures and solvolysis of tert-butyl bromide in methanol-chloroform mixtures have been studied. Solvent ionizing power of methanol-acetone mixtures were calculated by the Grunwald-Winstein equation and discussed the Y value variation caused by substrate changes. Y values based on 1-adamantyl tosylate is superion to others since it varies in wide range for methanol-acetone mixtures. It was found that the order of electrophilic assistance to leaving group is OTs > Cl > Br > I.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.615-621
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• 2013

Solvolyses of isobutyl chloroformate (4) in 43 binary solvent mixtures including highly aqueous media, water, $D_2O$, $CH_3OD$, 2,2,2-trifluoroethanol (TFE) as well as aqueous 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) solvents were performed at $45^{\circ}C$, in order to further investigate the recent results of D'Souza, M. $J^1$. et al.; solvolyses of 4 are found to be consistent with the proposed mechanism ($Ad_E$). The variety of solvent systems was extended to comprise highly ionizing power solvent media ($Y_{Cl}$ > 2.7 excepted for aqueous fluorinated solvents and pure TFE solvent) to investigate whether a mechanistic change occurs as solvent compositions are varied. However, in case of 18-solvent ranges having aqueous fluorinated solvent systems (TFE-$H_2O$ and HFIP-$H_2O$) and/or having $Y_{Cl}$ > 2.7 solvent systems, the solvent effect on reactivity for those of 4 are evaluated by the multiple regression analysis as competition with $S_N2$ - type mechanism. And in pure TFE and 97 w/w % HFIP solvents with high $Y_{Cl}$ and weak $N_T$, these solvolyses are understood as reactions which proceed through an ionization ($S_N1$) pathway.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.349-353
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• 1998

Solvolysis rates of substituted 2-aryl-1,1-dimethylethyl bromides (1) were determined in a variety of solvents such as aqueous mixtures of ethanol, acetone, 2,2,2-trifluoroethanol, and also mixtures of ethanol and TFE at 25 ℃, 35 ℃, and 45 ℃. The solvent effects were analyzed in terms of Winstein-Grunwald equation. The solvent effects of 1-4-MeO failed to give a single linear correlation against either Y or YCl (YBr), but exhibited a wide split pattern which could not be related to the solvent nucleophilicity. On the other hand 1-4-CH3 and 1-H gave a fairly good linearity. In the case of 1-4-MeO, a fairly good linearity was observed against YΔ defined from the solvolysis of 4-methoxyneophyl tosylate. It is assumed that resonance interaction between reaction site and aryl-π-system operates to give charge delocalization regardless of the different solvolysis mechanisms. The Hammett-Brown treatment of the solvolytic rate constant of compounds 1 was obtained non-linear two separated lines of - 1.06 to - 1.46, suggesting of mechanistic changeover from kc-ks to kΔ on going from electron-withdrawing to electron-donating substituents as a basis of 4-CH3 group.