• Bulletin of the Korean Chemical Society
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• v.30 no.2
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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).

• 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.23 no.1
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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).

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1897-1901
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• 2011

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. 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 mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• v.10 no.2
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• pp.172-177
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• 1989

Stereoselective solvolyses of optically active activated esters in the aggregate system of optically active polymeric surfactants containing imidazole and benzene moieties were performed. The catalyst polymers employed were copolymers of N-methacryloyl-L-histidine methyl ester (MHis) with N,N-dimethyl-N-hexadecyl-N-[10-(p-methacryloylo xyphenoxycarbonyl)-decyl]ammonium bromide(DEMAB). In the solvolyses of N-carbobenzoxy-D- and L-phenylalanine p-nitrophenyl esters (D-NBP and L-NBP) by polymeric catalysts, copoly(MHis-DEMAB) exhibited not only increased catalytic activity but also enhanced enantioselectivity as the mole ${\%}$ of surfactant monomers in the copolymers increased. The polymeric catalysts showed noticeable enantioselective solvolyses toward D- and L-NBP of the substrates employed. As the reaction temperature was lowered for the solvolyses of D- and L-NBP with the catalyst polymer containing 3.5 mole ${\%}$ of MHis, the increased reaction rate and enhanced enantioselectivity were observed. The coaggregative systems of the polymer and monomeric surfactants were also investigated. In the case of coaggregate system consisted of 70 mole ${\%}$ of cetyldimethylethylammonium bromide with polymeric catalyst showed maximum enantioselective catalysis, viz., $k_{cat}(L)/k_{cat}(D)$ = 2.85. The catalyst polymers in the sonicated solvolytic solutions were confirmed to form large aggregate structure by electron microscopic observation.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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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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• v.24 no.4
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• pp.431-436
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• 2003

Solvolytic rate constants at 25℃ are reported for solvolyses of cinnamyl bromide (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, and 2,2,2-trifluoroethanol. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol. Rate ratios in solvents of the same $Y_{Br}$ value and different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance (e.g. $[k_{40EW}/k_{97TFE}]$Y = 2.88, EW = ethanol-water). With use of the extended Grunwald-Winstein equation, the l and m values are similar to the values of 0.43 and 0.88 obtained for the solvolyses of 1 using the equation (see below) which includes a parameter (I) for solvation of aromatic rings. The magnitude of l and m values associated with a change of solvent composition predicts the $S_{N1}$ reaction mechanism rather than an $S_{N2}$ channel. Product selectivities (S), defined by S = [ether product]/[alcohol product]×[water]/[alcohol solvent] are related to four rate constants for reactions involving one molecule of solvent as nucleophile and another molecule of solvent as general base catalyst. A linear relationship between 1/S and molar ratio of solvent is derived theoretically and validated experimentally for solvolyses of the above substrates from water up 75% 1/S = $(k_{wa}/k_{aw})$([alcohol solvent]/[water]) + $k_{ww}/k_{aw}$ alcohol-water. The results are best explained by product formation from a “free” carbocation intermediate rather than from a solvent-separated ion pair.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2377-2381
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• 2007

Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.

• 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.20 no.5
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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.