• Journal of the Korean Chemical Society
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• v.54 no.3
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• pp.354-358
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• 2010

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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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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• v.3 no.1
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• pp.34-36
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• 1982

N-Methacryloyl-L-histidine and N-methacryloyl-L-histidine methyl ester were synthesized and polymerized to obtain polymeric catalysts with different functions. In the presence of each of these polymers the solvolytic reactions of p-nitrophenyl acetate (PNPA), 3-nitro-4-acetoxybenzoic acid(NABA), 3-acetoxy-N-trimethylanilinium iodide(ANTI) and 3-nitro-4-decanoyloxybenzoic acid(NDBA) were performed in 20% aqueous ethanol. For the purpose of comparison the low molecular weight analogs(LMWA's), L-histidine, L-histidine methyl ester and N-acetyl-L-histidine were also subjected to catalyze the solvolyses of above substrates. In the solvolysis of PNPA the polymeric catalysts exhibited lower activities than the LMWA's. However the ionic substrates, NABA and ANTI were solvolyzed at anomalous rate by polymeric catalyst, indicating that electrostatic effects are operative in the catalysis by polymers. Furthermore in the solvolysis of hydrophobic monomer NDBA, polymeric catalysts exhibited highly enhanced activities compared with the LMWA's implying that hydrophobic interaction can be the most important contribution to the high catalytic activity of imidazole-containing polymers.

• Bulletin of the Korean Chemical Society
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• v.11 no.2
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• pp.99-105
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• 1990

The Gutmann acceptor number(AN), solvatochromic parameters $({\alpha},{\beta}\;and\;{\pi}^{\ast})$ and hydrogen bonding equilibrium constants (KHB) were determined for three binary systems of methanol with 1,2-dimethoxyethane(DME), 1,2-dichloroethane(DCE) and pyridine (PYD). The solvolysis rate constants of t-butyl chloride, bromide and iodide were also determined in the three binary systems. Solvent properties and solvolysis rates have been discussed in the light of various solvent parameters. Solvolysis of t-butyl halides are most conveniently explained by the two-stage mechanism involving ion-pair intermediate with the ion-pair formation for chloride and ion pair dissociation for iodide as rate limiting.

• Bulletin of the Korean Chemical Society
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• v.8 no.5
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• pp.393-398
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• 1987

Solvolyses of 2-phenylethyl benzenesulfonates have been studied in methanol-water mixtures. Cross interaction constants, $\rho_{YZ}$, between substituents Y in the substrate and Z in the leaving group indicated somewhat closer distance between the two substituents than expected for the reaction system, which supported the involvment of phenyl group assisted pathway in the solvolysis. A smaller magnitude of $\rho_{YZ}$for MeOH was interpreted as the enhencement of solvent assisted pathway since MeOH is more nucleophilic than $H_2O$. Other selectivity parameters, Winstein coefficient m, Hammett's $\rho_Y^{+_Y}$ and $\rho_Z$, as well as activation parameters supported the participation of aryl assisted and aryl unassisted pathways in the $S_{N^2}$ process of the solvolysis reaction.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1186-1191
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• 1997

Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.599-605
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• 1992

Rate constants of methanolyses of para-Z-substituted benzenesulfonyl chlorides have been determined in various isodielectric solvent mixtures. A third-order kinetic behavior has been observed in the methanolysis of p-nitrobenzenesulfonyl chloride in methanol-nitromethane mixture from the correlation figure of logarithms of rate constants were plotted against Y-values based on solvolyses of 1-adamantyl tosylate. $S_N1$-$S_N2$ mixing mechanisms are favored by neutral or weak electron-donating and weak electron-withdrawing substituents of p-Z-substituted benzenesulfonyl chlorides in methanol-nitrobenzene mixture. While the methanolyses of para-Z-substituted benzenesulfonyl chlorides in methanol-ethylene glycol solvent mixture are appropriate for $S_N2$ mechanism from the mechanistic criterion by means of m-values.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1209-1214
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• 2010

Reactions of 2-methyl-2-chloroadamantane (1) in a variety of pure and binary solvents have been studied at various temperatures and pressures up to 80 MPa. The sensitivity (m) to changes in solvent ionizing power of the Grunwald-Winstein equation, and the activation volume (${\Delta}V^{\ddag}$) are calculated from the specific rates. An excellent linear relationship (R = 0.997) for 1, log (k/$k_0$) = $0.80Y_{Cl}$ + 0.11, and the activation volume, ${\Delta}V^{\ddag}$ = -15.2 ~ -10.2 $mL{\cdot}mol^{-1}$ were observed. These values are similar to those for solvolyses of 1-adamantyl halides over the full range of solvents, suggesting that the unimolecular mechanism involving ion pairs is rate-determining. These observations are also compared with those previously reported for the corresponding 1-adamantyl derivatives and chloroformate esters.

• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1268-1272
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• 2011

The specific rates of solvolysis of phenyl fluorothionoformate (PhOCSF, 1) have been determined in 22 pure and binary solvents at $10.0^{\circ}C$. The extended Grunwald-Winstein equation has been applied to the specific rates of solvolysis of 1 over the full range of solvents. The sensitivities (l = $1.32{\pm}0.13$ and m = $0.39{\pm}0.08$) toward the changes in solvent nucleophilicity and solvent ionizing power, and the $k_F/k_{Cl}$ values are similar to those previously observed for solvolyses of acyl haloformate esters, consistent with the addition step of an additionelimination pathway being rate-determining. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. The results are compared with those reported earlier for phenyl chloroformate and chlorothionoformate esters and mechanistic conclusions are drawn.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2263-2270
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• 2014

Solvolysis rate constants of 2-phenylethyl-(2-$PhCH_2CH_2OCOCl$, 1) and 2,2-diphenylethyl chloroformate (2,2-$Ph_2CHCH_2OCOCl$, 2), together with the previously studied solvolyses of ${\alpha}$- and ${\beta}$-substituted chloroformate ester derivatives, are reported in pure and binary solvents at $40.0^{\circ}C$. The linear free energy relationship (LFER) and sensitivities (l and m) to changes in solvent nucleophilicity ($N_T$) and solvent ionizing power ($Y_{Cl}$) of the solvolytic reactions are analyzed using the Grunwald-Winstein equation. The kinetic solvent isotope effects (KSIEs) in methanol and activation parameter values in various solvents are investigated for 1 and 2. These results support well the bimolecular pathway with same aspects. Furthermore, the small negative values of the entropies of activation of solvolysis of 1 and 2 in the highly ionizing aqueous fluoroalcohols are consistent with the ionization character of the rate-determining step, and the KSIE values of 1.78 and 2.10 in methanol-d indicate that one molecule of solvent acts as a nucleophile and the other acts as a general-base catalyst. It is found that the ${\beta}$-substituents in alkyl chloroformate are not the important factor to decide the solvolysis reaction pathway.