• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3587-3591
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• 2011

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3743-3747
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• 2011

Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${\rho}_Y$ is changed from unusual negative (${\rho}_Y$ < 0) with the weaker electrophiles to positive (${\rho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${\rho}_X$, ${\beta}_X$, and ${\rho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.

• 대한화학회지
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• 제31권6호
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• pp.534-541
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• 1987

$Hg^{2+}$이온의 존재하에서 $[CoCl(Hedta)]^-$ 착이온에 대한 에틸렌디아민(en) 치환반응기구에 대해서 uv 및 CD스펙트럼을 이용하여 조사하였다. 속도론적인 자료로부터 $Hg^{2+}$ 이온이 금속과 작용하여 첫 en이 치환될때는 회합반응 경로를 거치며 제2, 제 3의 en은 단계적으로 치환됨을 알 수 있었다. 그리고 생성된 $[Co(en)_3]^{3+}$의 광학순도로 부터 광학수율을 결정짓는 적절한 중간체를 제시하여 치환반응에 대한 새로운 반응경로를 제시하였다.

• 대한화학회지
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• 제34권1호
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• pp.10-18
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• 1990

파라-치환 브롬화 벤질의 가용매 분해반응을 DMSO-$H_2O$과 DMF-$H_2O$ 혼합용매계에서 속도론적으로 연구 하였다. 이 두 혼합용매계의 이온화력(Y)와 친핵도($N_{BS}$)를 결정하기 위하여 같은 혼합용매속에서 1-adamantyl halides, t-butyl halides 그리고 methyl tosylate를 가용매 분해반응시켰다. 각 DMSO-$H_2O$ 혼합용매에 대한 분광용매화 파라미터는 측정된 νmax를 Taft의 관계식에 대입시켜 결정하였다. 파라-치환 브롬화 벤질의 가용매 분해반응은 m, l값과 ${\beta},{\rho}_s$값으로 보아 전이상태에서 결합형성이 약간 우세한 경계반응 메카니즘으로 진행함을 알았다.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.968-973
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• 1998

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.389-393
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• 1987

The oxidation of carbon monoxide by gaseous oxygen on 0.53, 1.02, and 1.51 mol $\%$CoO-doped $-Fe_2O_3$ catalysts has been investigated in the temperature range from 340 to 480$^{\circ}C$ under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-order kinetics; the 0.5-order with respect to $O_2$ and the first-order with respect to CO. In the above temperature range, the activation energy is 0.34 $\pm$ 0.01 eV${\cdot}$$mol^{-1}$. The electrical conductivity of 0.53, 1.02, and 1.51 mol %CoO-doped $\alpha$-$Fe_2O_3$ has been measured at 350$^{\circ}C$ under various $P_{CO}and $P_{O_2}$. From the conductivity data it was found that $O_2$ was adsorbed on Vo formed by doping with CoO, while CO appeared essentially to be chemisorbed on the lattice oxygen of the catalyst surface. The proposed oxidation mechanism and the dominant defect were supported by the agreement between the kinetic data and conductivities.

• 대한화학회지
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• 제39권7호
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• pp.572-577
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• 1995

아세토니트릴 용매계에서 aryl 치환(Z)-benzoate류와 아민류의 반응속도를 15, 25, 및 35 $^{\circ}C$에서 분광학적 방법으로 구했다. 2차 반응속도 상수로부터 Hammett $\rho$값, Bronsted ${\beta}$값, 및 활성화 parameter를 구했으며 이들값과 M-O-F-J diagram 등의 해석으로부터 본 반응은 $S_AN$ 메카니즘으로 진행됨을 알 수 있었다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 하계학술대회 논문집
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• pp.620-623
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• 2001

The peculiarities of using Self-propagating High-temperature Synthesis (SHS) and solid state phase synthesis for production of high temperature superconductor materials are discussed. Oxide superconductors with general formula $ReBa_2$$Cu_3$$O_{7-x}$ (Re= Y, Yb, Sm, Nd) have been made with using barium oxide initial powder instead of traditional barium carbonate. X-ray powder diffraction showed a single phase orthorhombic perovskite structure was produced in all reactions. Phenomena observed during the grinding of the reactant mixture are presented. Mechano-chemical activation - as a pretreatment of the reactant mixture - strongly influences the kinetic parameters, the reaction mechanism, and the composition and structure of the final product.

• 대한화학회지
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• 제11권2호
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• pp.70-76
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• 1967

Structural changes attending polyacrylonitrile(PAN) upon heating and treating with nucleophilic reagents have been studied for some time and a few authors have studied on the thermal degradation, particularly on the characterization of degradation products in PAN. It is the purpose of this paper to report the kinetic study on the thermal degradation above $250^{\circ}C$ and make some suggestions as to the degradation process and mechanism in PAN. The degradation process in PAN is considered that three reactions are combined in two steps. Random chain scission accompanying the naphthylidine-type ring formation is the first step and the degradation of naphthylidine-type ring occurred as the next step. The reactions in the first step are competitive so that the maximum weight loss on pyrolysis of PAN, under such a condition that the degradation of naphthylidine-type ring is negligible, is depended on the relative reaction rate of these two competitive reactions.

• 대한화학회지
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• 제14권2호
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• pp.161-168
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• 1970

In order to obtain the more effective evidence, supporting the hypothesis which have been previously described by former report that pepsin (EC 3.4. 4.1) forms a hydrophobic bond with the nonpolar side chain of its substrate, the inhibitory effect of carboxylic acids(from formic acid to iso-butyric acid) on the activity of pepsin to the synthetic dipeptide, N-Carbobenzoxy-L-glutamyl-L-tyrosine, was discussed. The kinetic study showed that the inhibition by carboxylic acids was competitive. The Kidecreased with increasing size of the inhibitor molecule. The $-{\Delta}F^{\circ}$increased linearly with increasing number of carbon atoms in the hydrocarbon chain of the inhibitor. It was confirmed that the hydrophobic bond between more than one side chain of amino acid residues(phenylalanine) in the binding region of the active center of pepsin and the side chain of amino acid residues in the substrate was formed as the first step of its enzymic mechanism. The inhibitory effect of carboxylic acids was due to the competition of the hydrocarbon group of the carboxylic acids with the side chain of the substrate for the hydrophobic binding site(the side chain of phenylalanine) of the pepsin.