• Bulletin of the Korean Chemical Society
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• v.24 no.8
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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.

• Journal of the Korean Applied Science and Technology
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• v.26 no.2
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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.

• Journal of the Korea Institute of Military Science and Technology
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• v.2 no.1
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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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• v.38 no.1
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• pp.90-94
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• 1995

Post emergence herbicidal activities$(pI_{50})$ of X-substituted phenylvinylsulfone derivatives(S) in-vivo against rice(Oryza sativa L.), Barnyard grass(Echinochloa crus-galli) and Pickerelweed(Monochoria vaginalis Presl) were measured by the pot test under paddy conditions. The (S) showed herbicidal symptom rapidly with lower activity(average $pI_{50}=2.0$) as proherbicide, which was excellent tolerance to rice. The structure activity relationships(SAR) were analyzed using such a physicochemical parameters as hydrophobic$({\pi})$ and molecular orbital(MO) quantity by the multiple regression technique, and discussed with quantum pharmacology. The herbicidal activities were related to the hydrophobic$({\pi})$ effect of X-substituent and orbital(HOMO & LUMO) energy. In case of Pickerelweed, the effect was rationalized by parabolic function of ${\pi}$ constant, where the optimal value of ${\pi}$ was 1.10. An increase in hydrophobicity and negative orbital energy by the electron attracting X-substituent may contribute to the herbicidal activity. Based on results proposed from SAR analysis, the mode of herbicidal action could be assumed.

• Journal of the Korean Chemical Society
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• v.38 no.5
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• pp.391-396
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• 1994

The hydrolysis of $\alpha-benzoxystyrene(1)$ in strong acidic solution has been investigated kinetically. In perchloric acid concentration lower than 5.5 M($H_o$ < -3.0), hydration paramer $\omega$ = + 7.6, and $\Phi$ = + 0.54 were obtained. The solvent isotope effect $k_{H_2O}/K_{D_2O}$ is 0.72. The substituent effect was found to conform to the Hammett $\sigma^+$ constant with $\rho$ = -0.60. On the basis of these results and other evidence, the hydrolysis of the enol ester proceeds by $A_{AL}$2 type mechanism. In concentration greater than 5.5 M($H_o$ > -3.0), isotope effect, $k_{H_2O}/_{D_2O}$ is 3.32, substituent effect, $\rho$ is -1.60 and the rate is linear with the acidity function, $H_o$. Thus, the mechanism changes one involving initial, and rate-determining olefin protonation.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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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.

• Journal of the Korean Chemical Society
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• v.39 no.11
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• pp.842-847
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• 1995

The electrochemical reduction reactions of N '-aryl-N-alkyl-N-nitrosourea derivatives with a glassy carbon electrode were diffusion controlled and irreversible. The exchange kinetic constant ko values for reduction reaction of the N '-aryl-N-alkyl-N-nitrosoureas were at the range of $1.48{\times}10^{-6}{\sim}5.32{\times}10^{-7}\;cm/sec.$ The $k_0$ values for phenyl substituted on the aryl position were about 1.3∼2.8 times higher than that of other substituents. The same substituent for aryl groups on the both of N '-aryl-N-alkyl-N-nitrosourea and N '-aryl-N-(2-chloroethyl)-N-nitrosourea exhibited same value. The $E_p$ value was shifted to the negative direction as pH increased. The number of protons participated to the reduction was 4∼5, respectively. The substituent effect of aryl group on the reduction potential was not observed in this case.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.15 no.1
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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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• v.35 no.2
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• pp.87-91
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• 1992

Twenty-six N-substituted-5-chloro-1,3-dimethylpyrazole-4-carboxamide were synthesized and their antifungal activity against Rhizoctonia solani, Pyricularia oryzae, Botrytis cinerea and Colletotricum gleosporiodes was compared. N-phenyl-5-chloro-l,3-dimethylpyrazole-4-carboxamides having electron releasing group at the meta position of phenyl ring demonstrated good fugicidal activity against R. solani.