• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2443-2447
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate (7) and 4-nitrophenyl isonicotinate (8) with a series of cyclic secondary amines in $H_2O$ containing 20 mol % DMSO at $25.0^{\circ}C$. The Br${\o}$nsted-type plots for the reactions of 7 and 8 are linear with ${\beta}_{nuc}=0.90$ and 0.92, respectively, indicating that the reactions proceed through a stepwise mechanism with expulsion of the leaving group occurring in the rate-determining step. Comparison of the reactivity of 7 and 8 with that of 4-nitrophenyl benzoate (2a) and 4-nitrophenyl picolinate (6) has revealed that their reactivity toward the amines increases in the order 2a < 7 < 8 < 6, although the reactions of these substrates proceed through the same mechanism. Factors that control reactivity and reaction mechanism have been discussed in detail (e.g., inductive and field effects, H-bonding interaction, solvent effect, etc.).

• Bulletin of the Korean Chemical Society
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• v.26 no.7
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• pp.1017-1024
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• 2005

Elimination reactions of $XC_6H_4CH_2CO_2C_6H_3-2-Y-4-NO_2$ have been studied under various conditions. When X was moderately electron-withdrawing, Y = H, and base-solvent was $R_2$NH-MeCN, the reaction proceeded by the E2 mechanism via an E1cb-like transition state. Concave downward curve was noted in the Hammett plots. When X = 4-$NO_2$, Y = Cl, $CF_3,\;NO_2$, and the base-solvent was ${R_2NH/R_2NH_2}^+$ in 70 mol % MeCN(aq), the reaction proceeded by the E2 mechanism. The mechanism changed to a competing E2 and E1cb when X = 4-$NO_2$ and Y = H, MeO, and to the E1cb when X = 2,4-($NO_2)_2$, and Y = $NO_2$. From these results, a plausible pathway of the change of the mechanism from E2 to the E1cb extreme is proposed.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2909-2912
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• 2009

The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H$_2$O although they are 7 to 9 pK$_a$ units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small ${\beta}_{nuc}$ values, i.e., ${\beta}_{nuc}$ = 0.29 in H$_2$O and ${\beta}_{nuc}$ = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small ${\beta}_{nuc}$ value also supports the conclusion drawn from the study of kinetic isotope effect.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4117-4121
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• 2012

The solvolysis rate constants of allyl chloroformate ($CH_2=CHCH_2OCOCl$, 3) in 30 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 sensitivity values of $0.93{\pm}0.05$ and $0.41{\pm}0.02$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.5 to 13.4 $kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -34.4 to -37.3 $cal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, $k_{MeOH}/k_{MeOD}$) of 2.16 was also in accord with the $S_N2$ mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.

• Proceedings of the Materials Research Society of Korea Conference
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• 1999.11a
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• pp.132-132
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• 1999

• Bulletin of the Korean Chemical Society
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• v.24 no.6
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• pp.691-694
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• 2003

We report a quantum wavepacket study on the characteristic bimodal translational energy distribution of photostimulated desorbed Xe from an oxidized silicon (001) surface observed by Watanabe and Matsumoto, Faraday Discuss. 117 (2000) 203. We have simulated the theoretical translational energy distributions based on wavepacket calculations with a sudden transition and averaging model to reproduce the experiment. We discuss the desorption mechanism and suggest a very strong position dependence of the deexcitation processes for Xe/oxidized Si(001).

• Proceedings of the Korea Society of Environmental Toocicology Conference
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• 2003.05a
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• pp.166-166
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• 2003

In terms of the risk assessment, qualitative and quantitative informations are needed to estimate the exposures of environmental pollutants, which may be potentiality of risks, and those are the information about the changes caused by the chemical transportation among environmental media and transformation in environmental media by duration. The various fate mechanism of chemical is possible for estimation of chemical concentration in environmental media. Since there are limitations in measuring the change of chemical concentration within all medium according to the time period, estimating method through modeling are developed.

• Rapid Communication in Photoscience
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• v.2 no.1
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• pp.31-33
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• 2013

The irradiation of electron-beam onto bis-(diphenylphosphino)methane, ethane, propane and butane initiated phenyl-shift from a phosphine to another phosphine atom and subsequent fragmentation resulted in the formation of triphenylphosphine derivative as key intermediate. The mechanism of those processes is speculated.

• Bulletin of the Korean Chemical Society
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• v.27 no.4
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• pp.503-507
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• 2006

The rhodium(II)-catalyzed reactions of diazo compound derived from Meldrum's acid with a variety of styrenes have been examined. These reactions provide a rapid route to the preparation of cyclopropanes with a variety of substituents on the benzene ring. The mechanistic pathway for the formation of these products has been also described in terms of a stepwise mechanism.

• Bulletin of the Korean Chemical Society
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• v.6 no.2
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• pp.115-118
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• 1985

The oxidation of hydrazobenzene by oxygen in methanol solution is catalysed by Co(3MeOsalen) which is a synthetic oxygen carrier. The products are trans-azobenzene and water. The rate of the reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a ternary complex of catalyst, hydrazobenzene and oxygen has been proposed.