• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.577-580
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• 1999

Solvolyses of phenyl chlorothionoformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of firstorder rate constants for phenyl chlorothionoformate with Ycl (based on 2-adamantyl chloride) show a dispersion phenomenon, and also the extended Grunwald-Winstein plots show a poor correlation for the solvolyses of phenyl chlorothionoformate. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original and extended Grunwald-Winstein correlations. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by the conjugation between the reaction center and the aromatic ring in the vicinity of the reaction center. This study has shown that the magnitude of l and m values associated with a change of solvent composition leads to predict the SN2 transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed SN2 mechanism.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.661-664
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• 2005

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3366-3370
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• 2010

The specific rates of solvolysis of t-butyl fluoroformate (1) have been measured at $40.0^{\circ}C$ in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation, with incorporation of the solvent nucleophilicity and the solvent ionizing power, is applied. The actual values are very similar to those obtained in earlier studies of the solvolyses of isopropyl chloroformate and ethyl chlorothioformate in the more ionizing and least nucleophilic solvents, which are believed to proceed by an ionization pathway. The small negative values for the entropies of activation are consistent with the ionization nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding primary and secondary alkyl haloformate esters.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.378-382
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• 2009

Rates of solvolyses of benzhydryl chloride ($Ph_2$CHCl, 1) and benzhydryl bromide ($Ph_2$CHBr, 2) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, 2,2,2-trifluoroethanol (TFE) and acetone are reported. Solvolyses were also carried out in TFE-ethanol mixtures. Application of the extended Grunwald-Winstein equation led to l value of 1.19 (1), 1.29 (2) and m value of 1.00 (1), 0.77 (2), correlation coefficient of 0.965 (1) and 0.970 (2). Sensitivities (l = 1.19 (1), 1.29 (2) and m = 1.00 (1), 0.77 (2)) were similar to those obtained for several previously studied solvolyses, in which an $S_N$2 pathway is proposed for the solvolyses of benzhydryl halides ($Ph_2$CHX, X = Cl or Br).

• 대한화학회지
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• 제61권1호
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• pp.25-28
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• 2017

Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.499-504
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• 2012

The specific rates of sovolysis of 4-methylthiophene-2-carbonyl chloride (1) have been determined in 26 pure and binary solvents at $25.0^{\circ}C$. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol binary mixtures. Comparison of the specific rates of solvolyses of 1 with those for p-methoxybenzoyl chloride (2) in terms of linear free energy relationships (LFER) are helpful in mechanistic considerations, as is also treatment in terms of the extended Grunwald-Winstein equation. It is proposed that the solvolyses of 1 in binary aqueous solvent mixtures proceed through an SN1 and/or ionization (I) pathway rather than through an associative $S_N2$ and/or addition-elimination (A-E) pathway.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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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.

• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1927-1931
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• 2008

Rate of solvolysis of diphenylthiophosphinyl chloride in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE) or 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Solvolyses were also carried out in TFE-ethanol mixtures. For five representative solvents, studies were made at several temperatures and activation parameters determined. The 29 solvents gave a reasonably precise extended Grunwald-Winstein equation plot, correlation coefficient (R) of 0.933, which improved to 0.983 when the four TFE-ethanol points were excluded. The sensitivities (l = 1.00 and m = 0.64) were similar to those obtained for dimethyl phosphorochloridate and phosphorochloridothionate and diphenylphosphinyl chloride (1). As with the four previously studied solvolyses, an $SN_2$ pathway is proposed for the solvolyses of diphenylthiophosphinyl chloride. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for an $S_N2$ reaction.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2413-2417
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• 2011

The specific rates of solvolysis of 1- naphthyl chloroformate (1-NaphOCOCl, 1) and 2-naphthyl chloroformate (2-NaphOCOCl, 2) have been determined in a wide range of solvents at 2.0 and 10.0$^{\circ}C$. These give a satisfactory correlation over the full range of solvents when the extended (two-term) Grunwald-Winstein equation is applied. The sensitivities (l and m-values) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) are similar to those reported previously for solvolysis of phenyl chloroformate, which has been suggested to proceed through an addition-elimination mechanism with the addition step being rate determining. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations were also compared with those previously reported for phenyl chloroformates and naphthoyl chlorides.

• Bulletin of the Korean Chemical Society
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• 제23권1호
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• pp.123-131
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• 2002

Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).