• Journal of the Korean Chemical Society
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• v.59 no.5
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• pp.373-378
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• 2015

The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH₃CH₂CH₂CH₂O)₂POCI, 1) in 28 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 the sensitivities values of 1.40 and 0.42 for l and m, respectively. These l and m values can be considered to support an S_N2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH^≠ (8.0 to 15.9 kcal·mol⁻¹ ) values and large negative ΔS^≠ (−25.8 to −53.1 cal·mol⁻¹ ·K⁻¹ ) values, the Kivinen’s n values (0.9~1.7), and the solvent kinetic isotope effect (1.62).

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.296-300
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• 1986

The pseudo-first order rate constants have been obtained for the solvolysis of pseudo-saccharinechloride in MeOH-$H_2O$, EtOH-$H_2O$, MeOH-MeCN and MeOH-$(Me)_2$CO solvents mixtures at various temperatures. Values of n and m in the Kivinen and Grunwald-Winstein plots, respectively, have been determined and the Taft's solvatochromic parameters were obtained; based on these solvent effect parameters as well as on the activation parameters it was concluded that reaction proceeds via an $S_N2$ mechanism.

• Journal of the Korean Chemical Society
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• v.27 no.2
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• pp.95-101
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• 1983

The pseudo-first order rate constants have been obtained for the solvolysis of benzoyl cyanide in various aqueous solvent mixtures and ethanol-trifluoroethanol mixtures at 1, 5, 10, 15 and $20^{\circ}C$. Values of n in the Kivinen polt, m values of Grunwald-Winstein polt, $\beta$ values of Leffler relationship and values of m and l in the extended Grunwald-Winstein polt have been calculated and studied the transition state variation caused by solvent changes using the More O'Ferrall polt and quantum mechanical approach. It has been shown that the reaction proceed via the associative $S_N2$ mechanism, using the transition state parameters and quantum mechanical model approach.

• 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.

• 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.30 no.1
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• pp.3-8
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• 1986

The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.