• Bulletin of the Korean Chemical Society
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• 제24권8호
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• pp.1135-1140
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• 2003

The kinetics and mechanism of the pyridinolysis $(XC_5H_4N)$ of Y-aryl phenyl isothiocyanophosphates (1;$(YC_6H_4O)\;(C_6H_5O)$P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the $^-NCS$ group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or $pK_a$(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx.

• 한국응용과학기술학회지
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• 제26권2호
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• pp.132-142
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• 2009

The benzophenone derivatives(4-$CH_3O$-4'-$NO_2$ and 3,4'-di-$NO_2$) are synthesized by the Fridel-Craft acylation and the nitration method. Electrochemical redox potentials of the benzophenone derivatives (4-$CH_3O$, H, 3-Cl, 3-$NO_2$, 4-$NO_2$, 4-$CH_3O$-4'-$NO_2$, 3,4'-di-$NO_2$) are measured by using cyclic voltammometry. In the relationship of summing Hammett value and redox potential, we find a proportional constant$(\rho)$ that shows a good relation with an electrochemical property and a reactivity of the benzophenone derivatives. The benzophenone substituted with the electron donating groups(4-$OCH_3$ and 4-$OCH_3-4'-NO_2$) are higher the energy in the LUMO level, then increasing a band-gap energy$(E_g)$, their $E_gs$ are obtained as a 3.94 eV and 3.59 eV, respectively.

• 한국군사과학기술학회지
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• 제2권1호
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• pp.73-81
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• 1999

Four bis-iodosobenzoic acid derivatives have been synthesizd in 5 steps following literature methods from 5-hydroxyantranilic acid; 1) diazotization and iodination, 2) acid protection, 3) tosylate substitution, 4) acid deprotection, 5) oxidation of iodo-substituent to iodoso group. Catalytic effects of new 5,5'-tri-, tetra-, deca-, polyethyleneglycoxy- bis(2-iodosobenzoic acid) on hydrolysis reactions of PNPDPP(p-nitrophenyl diphenyl phosphate), sarin and soman have been measured to determine the role of ethyleneglycoxy substituents as phase transfer catalysts. At $25{\pm}0.2^{\circ}C$, pH 8.0, and cetyltrimethyl ammonium chloride(CTACl) micelle solution condition, bis-IBA derivatives hydrolyzes PNPDPP with maximum pseudo-first order rate constant($K_{obsd}^{max}$) of 0.32035 ~ 0.13659 $sec^{-1}$, which corresponds to 2~18 times rate increase than those of unsubstituted o-IBA[iodosobenzoate($K_{obsd}^{max}=0.0645sec^{-1}$), iodoxybenzoate ($K_{obsd}^{max}$ = $0.0178 sec^{-1}$)]. At the similar condition for PNPDPP hydrolysis, bis-IBA derivatives also act as efficient catalysts for hydrolytic cleavage of nerve agents such as sarin and soman. Hydrolysis rate constant with 5,5'-polyethyleneglycoxy- bis(2-iodosobenzoic acid) shows 7 times increase than that of simple 5-hydroxy-2-iodosobenzoic acid.

• Applied Biological Chemistry
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• 제38권1호
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• pp.90-94
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• 1995

벼(Oryza sativa L.)를 위시하여 논잡초인 피(Echinochloa crus-galli)와 물달개비(Monochoria vaginalis Presl)에 대한 phenylvinylsulfone유도체(S)들의 제초활성을 측정 한 바, 발아 전후에 벼(Oryza sativa L.)이외의 잡초에 대하여 현저하게 속효성이고 선택적인 제초활성을 나타내었다. (S)의 phenyl기에 X-치환기가 변화함에 따른, 구조와 제초활성과의 관계(SAR)를 양자 약리학적 방법으로 분석한 바, 피의 경우에는 ${\pi}$상수가 클수록(${\pi}$<0) 그리고 LUMO가 음의 값으로 증가할수록 제초활성이 증가 하였다. 한편, 물달개비의 경우에는 ${\pi}$상수의 적정값(optimal value)이 1.10이었으므로 이 값에 가까울수록 제초활성이 클 것이며 HOMO에 의존적임을 알 수 있었다. 따라서 X-치환기로 전자끌게가 치환됨으로써 ${\pi}$상수가 크고(${\pi}$<01.10) 음의 값으로 HOMO와 LUMO가 클수록 고활성을 나타낼 수 있는 화합물의 조건들에 대하여 검토되었으며 실험사실을 합리적으로 설명할 수 있는 제초활성 작용기작(mode of action)을 가정 하였다.

• 대한화학회지
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• 제38권5호
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• pp.391-396
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• 1994

강산성 용액에서 $\alpha$-벤족시스티렌(1)의 가수분해를 속도론적으로 다루었다. 과염소산이 5.5M보다 낮은 농도($H_o$ < -3.0)에서 수화파라메타 $\omega$ = + 7.6, $\Phi$ = + 0.54를 얻었다. 용매동위원소효과 $k_{H_2O}/k_{D_2O}$는 0.72였고, Hammett $\sigma^+$ 상수에 대한 치환기 효과 $\rho$ = -0.60이었다. 이 결과와 다른 증거로부터 이 산도 범위에서 엔올에스테르의 가수분해는 $A_{AL}$2 형태의 메카니즘에 의해 진행되었다. 과염소산 농도가 5.5 M 이상에서는 동위원소효과, $k_{H_2O}/_{D_2O}$는 3.32이었고, 치환기 효과, $\rho$=-1.6이었으며, 속도상수는 산도함수, $H_o$에 비례하였다. 따라서 반응메카니즘은 변하여 올레핀이 양성자화되는 첫단계가 속도결정단계가 된다.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2135-2138
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• 2014

A kinetic study is reported for the SNAr reaction of 1-Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1h) with OH- in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The second-order rate constant ($k_{OH^-}$) increases as the substituent Y in the leaving group changes from an electron-donating group (EDG) to an electronwithdrawing group (EWG). The Br${\o}$nsted-type plot for the reactions of 1a-1h is linear with ${\beta}_{lg}$ = -0.16, indicating that the reactivity of substrates 1a-1h is little affected by the leaving-group basicity. A linear Br${\o}$nsted-type plot with ${\beta}_{lg}=-0.3{\pm}0.1$ is typical for reactions reported previously to proceed through a stepwise mechanism in which formation of a Meisenheimer complex is the rate-determining step (RDS). The Hammett plot correlated with ${\sigma}_Y{^{\circ}}$ constants results in a much better correlation than that correlated with ${\sigma}_Y{^-}$constants, implyng that no negative charge is developing on the O atom of the leaving group (or expulsion of the leaving group is not advanced at all in the TS). This excludes a possibility that the $S_NAr$ reaction of 1a-1h with $OH^-$ proceeds through a concerted mechanism or via a stepwise pathway with expulsion of the leaving group being the RDS. Thus, the current reactions have been concluded to proceed through a stepwise mechanism in which expulsion of the leaving group occurs rapidly after the RDS.

• 대한화학회지
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• 제39권11호
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• pp.842-847
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• 1995

유리질 탄소전극을 사용하여 조사한 몇가지 N'-aryl-N-alkyl-N-nitrosourea 유도체들의 전기화학적 환원반응은 확산지배적이고 비가역적인 반응이었다. 이들 유도체들의 환원 반응시의 교환속도 상수 $k_0$값은 $1.48{\times}10^{-6}{\sim}5.32{\times}10^{-7}\;cm/sec.$의 값을 나타내었었다. Aryl기 및 alkyl기의 치환기에 따른 교환속도상수는 $k_0$ N'-aryl-N-alkyl-N-nitrosourea 에서 aryl기가 phenyl일 경우, 다른 치환기보다 $k_0$값이 1.3-2.8배였다. N'-aryl-N-alkyl-N-nitrosourea 와 N'-aryl-N-(2-chloroethyl)-N-nitrosourea의 두 화합물에서 aryl기의 치환기가 같을 경우는 비슷한 값을 나타내었다. N'-aryl-N-methyl-N-nitrosourea 유도체는 pH값이 높아짐에 따라 $E_p$값이 음전위쪽으로 이동하며 각 환원 반응에 참여한 $H^+$의 수는 4-5개였다. 이경우 aryl기의 치환기 효과는 환원전위에 크게 영향을 미치지 않는 것으로 나타났다.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1329-1332
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• 2014

The kinetic studies on the reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide. The free energy correlations with X in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of ${\rho}_{XZ}$ implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The biphasic concave upward free energy relationships with X are rationalized by a change in the nucleophilic attacking direction from frontside with the strongly basic pyridines to backside with the weakly basic pyridines.

• 한국수소및신에너지학회논문집
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• 제15권1호
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• pp.12-22
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• 2004

In order to evaluate the potential of partial hydrocarbon substitution to improve the safety of hydrogen use in general and the performance of internal combustion engines in particular, the outward propagation and development of surface cellular instability of spark-ignited spherical premixed flames of mixtures of hydrogen, hydrocarbon, and air were experimentally studied at NTP (normal temperature and pressure) condition in a constant-pressure combustion chamber. With propane being the substituent, the laminar burning velocities, the Markstein lengths, and the propensity of cell formation were experimentally determined, while the laminar burning velocities and the associated flame thicknesses were computed using a recent kinetic mechanism. Results show substantial reduction of laminar burning velocities with propane substitution, and support the potential of propane as a suppressant of both diffusional-thermal and hydrodynamic cellular instabilities in hydrogen-air flames.

• Applied Biological Chemistry
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• 제35권2호
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• pp.87-91
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• 1992

생리활성을 갖는 신규물질탐색의 일환으로 26종의 N-치환-5-chloro-1,3-dimethylpyra-zole-4-carboxamide 화합물을 합성하고, 이들 구조를 $^1H-NMR$로 확인하였다. 이들 유도체들을 Rhizoctonia solani, Botrytis cinerea, Pyricularia oryzae 및 Colletotricum gleosporiodes에 대한 in vitro에서의 균사생육억제효과를 검정한 결과 electron releasing group으로 meta 치환된 aniline의 carboxamide가 R. solani에 대해 12.5 ppm 수준에서 70% 이상의 살균효과를 보여주었다.