• Bulletin of the Korean Chemical Society
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• v.20 no.5
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• pp.573-576
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• 1999

The rate constants and kinetic solvent isotope effects (KSIE, KMeOH/kMeOD) for solvolyses of para-substituted phenylchloroformates in CH3OH, CH3OD, H2O, D2O, 50% D2O-CH3OD were determined at 15.0 and 25.0℃ using conductometric method. Kinetic solvent isotope effects for the solvolyses of para-substituted phenyl chloroformates were 2.39-2.51, 2.21-2.28, and 1.67-1.69 for methanol, 50% aqueous methanol, and water, respectively. The slopes of Hammett plot for solvolysis of para-substituted phenyl chloroformates in methanol, 50% aqueous methanol, and water were 1.49, 1.17 and 0.89, respectively. The Hammett type plot of KSIE, log (KSIE) versus p, can be a useful mechanistic tool for solvolytic reactions. The slopes of such straight lines for para-substituted phenyl chloroformates are almost zero in methanol, 50% aqueous methanol, and water. It was shown that the reaction proceeds via an associative SN2 and/or general base catalysis addition-elimination (SAN) mechanism based on activation parameters, Hammett p values, and slopes of Hammett type plot of KS-IE.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.3003-3008
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• 2011

Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

• Journal of the Korean Chemical Society
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• v.63 no.4
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• pp.233-236
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• 2019

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol-water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ 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.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2285-2289
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• 2014

The solvolysis rate constants of 5-dimethylamino-naphthalene-1-sulfonyl chloride ($(CH_3)_2NC_{10}H_6SO_2Cl$, 1) in 31 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 $0.96{\pm}0.09$ and $0.53{\pm}0.03$ for l and m, respectively; the correlation coefficient value was 0.955. These l and m values can be considered to support an $S_N2$ reaction pathway having a transition state (TS) structure similar to that of the benzenesulfonyl chloride reaction. This interpretation is further supported by the activation parameters, i.e., relatively small positive ${\Delta}H^{\neq}$ (12.0 to $15.9kcal{\cdot}mol^{-1}$) and large negative ${\Delta}S^{\neq}$ (-23.1 to $-36.3cal{\cdot}mol^{-1}{\cdot}K^{-1}$) values, and the solvent kinetic isotope effects (SKIEs, 1.34 to 1.88). Also, the selectivity values (S = 1.2 to 2.9) obtained in binary solvents are consistent with the proposed mechanism.

• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.699-703
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• 2004

Solvolyses of isopropylsulfonyl chloride (IPSC) in water, D_2O,\;CH_3OD$, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45$^{\circ}C$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of IPSC with $Y_{Cl}$ (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small slope (m < 0.30). The extended Grunwald-Winstein plots for the solvolysis of IPSC show better correlation. The kinetic solvent isotope effects determined in water and methanol are in consistent with the proposed mechanism of the general base catalyzed and/or $S_AN/S_N2$ reaction mechanism for IPSC solvolyses based on mass law and stoichiometric solvation effect studies.

• 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.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.22 no.8
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• pp.842-846
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• 2001

Solvolyses of N-methyl-N-phenylcarbamoyl chlorides in aqueous binary mixtures of acetone, ethanol, methanol and in water, D2O, and 50% D2O-CH3OD are investigated at 25.0 $^{\circ}C.$ The Grunwald-Winstein plots of first-ord er rate constants for N-methyl-N-phenylcarbamoyl chlorides with YCl (based on 2-adamantyl chloride) show a dispersion phenomenon. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original Grunwald-Winstein and extended Grunwald-Winstein correlations for the solvolyses of N-methyl-N-phenylcarbamoyl chlorides. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the dissociative SN2 transition state. The kinetic solvent isotope effects determined in deuterated water are consistent with the proposed mechanism of the general base catalyzed and/or a dissociative SN2 mechanism channel for N-methyl-N-phenylcarbamoyl chlorides solvolyses.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3657-3664
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• 2012

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.