• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.511-516
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• 1992

The x-values of the nonstoichiometric compound YbO$_x$ have been measured in a temperature range of 600 to 1150$^{\circ}C$ under oxygen partial pressure of 1.00 ${\times}$ 10$^{-2}$ atm∼atmospheric air pressure. The values are varied between 1.55453 and 1.60794 in the conditions. The enthalpy of the formation for x' in YbO$_{1.5＋x'}$(${\Delta}$H$_f$) was 1.55, 1.18, and 1.05 kJ/mol under the above conditions, respectively. The electrical conductivities of the oxides or ${\sigma}$ have been measured in the temperature range from 600 to 1100$^{\circ}C$ under oxygen partial pressure of 1.00 ${\times}$ 10$^{-5}$ ∼ 2.00 ${\times}$ 10$^{-1}$ atm. They varied from 10$^{-9}$ to 10$^{-5}$ ohm$^{-1}$ cm$^{-1}$ within the semiconductor range. The Arrhenius plots of the electrical conductivities show a linearity and the activation energy for the conduction was about 1.7eV. The oxygen partial pressure dependence of the conductivity or 1/n value increases with the pressure. The nonstoichiometric conduction mechanism of the oxide was discussed in terms of the x values, ${\sigma}$ values, and the thermodynamic data.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.329-334
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• 1991

The x values and electrical conductivity of the nonstoichiometric compound NbO$_x$ have been measured in a temperature range 700$^{\circ}C$ to 1100$^{\circ}C$ under oxygen partial pressure of 2 ${\times}$ 10$^{-1}$ ∼ 1 ${\times}$ 10$^{-5}$ atm. The NbO$_x$ is a stoichiometrical compound of Nb$_2$O$_5$ under oxygen partial pressure higher than 1.0 ${\times}$ 10$^{-2}$ atm at the above temperature range. The x values were found to vary between 2.48491 and 2.49900 in a temperature range 700$^{\circ}C$ to 1100$^{\circ}C$ under oxygen partial pressure lower than 1 ${\times}$ 10$^{-3}$ atm. The enthalpy of the formation for x' in NbO$_{2.50000-x'}$(${\Delta}H_f$) increased of 15.98 to 17.26 kcal/mol under the conditions. The electrical conductivity (${\sigma}$) of the oxide varied from 10$_4$ to 10$_1$ ohm$_1$cm$_1$ in the above conditions. The activation energy for the conduction was about 1.7 eV. The oxygen pressure dependency of the conductivity (or 1/n value) was about -1/4. The nonstoichiometric conduction mechanism of the oxide has been discussed with the x' values, the ${\sigma}$ values, and the thermodynamic data.

• Analytical Science and Technology
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• v.7 no.3
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• pp.379-386
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• 1994

The elution behaviors in reversed-phase liquid chromatography were investigated thermodynamically for 2-hydroxy-arylazopyrazolone chelates with Ni(II), Cu(II), Co(III), Cr(III) on Novapak $C_{18}$ column. There was a good linear dependence of the capacity factor(k') on the variations of column temperature in van't Hoff plot. From this result, it was confirmed that the retention mechanism of these chelates in the reversed phase liquid chromatography system was invariant under the condition of various temperatures. For the most cases of the chelates studied, the dependence of capacity factor(1n k') on enthalpy$(-{\Delta}H)^{\circ}$, calculated by van't Hoff plot showed a good linearity(r=0.980~0.999) except [Pm(2-OH_(5-Cl)PaPz](r=0.787) and also the compensation temperatures(${\beta}$) showed constant values. The range of compensation temperature values calculated from the slope of $-{\Delta}H^{\circ}$ vs 1n k' plots was 374.3~806.9K. It was suggested that the retention of metal-2-hydroxy-arylazopyrazolone chelates in the reversed phase liquid chromatography system was largely affected by the hydrophobic effect.

• Applied Biological Chemistry
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• v.39 no.1
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• pp.70-76
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• 1996

A series of the herbicidal pyridylsulfonyl areas, none substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(2-pyridylsulfonyl) urea, 3 and 3-trifluoromethyl substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl) urea, 5(Flazasulfuron) were synthesizied and the rate of hydrolysis of their has been studied in 25%(v/v) aqueous dioxane at $45^{\circ}C$. From the results of solvent effect($m{\ll}1,\;n{\ll}3\;&\;{\mid}m{\mid}{\ll}{\mid}{\ell}{\mid}$), thermodynamic parameter (${\Delta}S^{\neq}=0.54{\sim}\;-2.19\;e.u.\;&\;{\Delta}H^{\neq}=0.025\;Kcal.mol.^{-1}$), hydrolysis product analysis, $pK_a$ constant(3: 4.9 & 5: lit.4.6) and the rate equation, a marked difference in the kinetics of the reaction of 3 and 5(Flazasulfuron) was observed. It may be concluded that the hydrolysis of 5 proceeds through the $A-S_N2Ar$ reaction via conjugate acid$(5H^+)$ below pH 7.0, whereas, above pH 9.0, the hydrolysis proceeds through irreversibly $(E_1)_{anion}$ and reversibly $(E_1CB)_R$ mechanism via conjugate base(CB), respectively. But in case of 5, $A-S_N2Ar,\;(E_1)anion\;and\;(E_1CB)_R$ mechanism involved Smile rearrangement. The mate of rearrangement of 5 to a 3-trifluoromethyl-2-pyridylpyrimidinyl urea(PPU) in acid and 3-trifluoromethyl-2-pyridyl-4.6-dimethoxypyridinyl amine (PPA) in base was increased about 3.5 times by the introduction of trifluoromethyl group in the 3-position on the 2-pyridyl ring. From the basis of these findings, a possible mechanism for the hydrolysis of 5 was proposed and discussed.

• The Korean Journal of Pesticide Science
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• v.2 no.1
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• pp.46-52
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• 1998

The hydrolysis rate of insecticidal buprofezin(IUPAC : tert-butylimino-3-isopropyl-5-phenylperhydro-1,3,5-thiadiazin-4-one) in the range of pH 2.0 and 12.0 have been examined in 15%(v/v) aqueous dioxane at $45^{\circ}C$. The hydrolysis mechanism of buprofezin is proposed from the pH-effect, solvent effect(${\ell}{\gg}m$), thermodynamic parameter(${\Delta}H^{\neq}$=11.12 $Kcal{\cdot}mol^{-1}$ &, ${\Delta}S^{\neq}=5.0e.u.$), rate equation and hydrolysis product, l-isopropyl-3-phenyl urea. General acid catalyzed hydrolysis and specific acid catalyzed($k_{H3O+}$) hydrolysis through $A-S_{E}2$ and A-2(or $A_{AC}2$) reaction mechanism with orbital-control reaction proceed below pH 8.0 and above pH 9.0, the nucleophilic addition-elimination, $Ad_{N}-E$ mechanism via tetrahedral($sp^{3}$) intermediate is initiation by general base catalyzed($k_{H2O}$) reaction. Buprofezin was more stable in alkaline ($k=10^{-8}sec.^{-1}$) than acid solutions from the sigmoid pH-rate profile. And the half-life($t=\frac{1}{2}$) of hydrolysis reaction in neutral aqueous solution(pH 7.0) at $45^{\circ}C$ was about 3 months.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.119-130
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• 1993

The stereochemistry of 1,3-thiazolidine sulfoxides 1 in which 3 chiral centres are present in a molecule was elucidated by deuterium exchange and trapping reactions. 3-Acetoxy-1,3-thiazolidines 5 was oxidized to 6 and 8, corresponding $\alpha$-cis 10, $\alpha$-trans 11, $\beta$ -cis 12, and $\beta$ -trans 13 isomers were separated from their diasteromeric mixtures. Sulfoxide 10 was isomerized to more thermodynamically stable isomer 13 under neutral conditions in refluxing benzene or toluene. The methyl hydrogens of 2-methyl group in the sulfoxide 13 and those of the sulfoxide 11 were deuterated by the deuterium incorporation reactions. The intermediate sulfenic acids 25 and 26 derived from the sulfoxides 10 and 12 via sigmatropic rearrangement were trapped by 2-mercaptobenzothiazole (2-MBT) to give disufides 27 and 28 respectively. However, the sulfoxides 11 and 13 were transformed to ring expansion product dihydro-1,4-thiazine 29 under the same reaction conditions. In the presence of acid catalyst, the sulfoxides 10, 11, and 12 were converted to dihydro-1,4-thiazine 29 through the sulfoxide 13 quantitatively. The mechanisms of isomerization of sulfoxides and the formation of 29 were also discussed.

• Journal of the Korean Chemical Society
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• v.37 no.12
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• pp.1035-1046
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• 1993

Some iron(III)porphyrin complexes were prepared, and identified by the spectroscopic methods. Elution behavior of iron(III)porphyrin complexes was investigated by reversed-phase HPLC. The optimum conditions for the separation of iron(III)porphyrin complexes were examined with respect to flow rate and mobile phase strength. These complexes were successfully separated on NOVA-PAK $C_{18}$ column using methanol / water(95/5) for $[T_pCF_3PP)Fe(R)]$ and methanol / water (98/2) for $[(P)Fe(C_6F_5)]$ as a mobile phase. It was found that these complexes were largely eluted in an acceptable range of capacity factor value ($0{\leq}logk'{\leq}1$). The dependence of the capacity factor (k') on the volume fraction of water in the binary mobile phase as well as the dependence of k' on the liquid-liquid extraction distribution ratio$(D_c)$ in methanol-water / n-pentadecane extraction system showed a good linearity. It means that the retention of iron(III)porphyrin complexes on NOVA-PAK $C_{18}$ column is largely due to the solvophobic effect. Also, there was a good linear dependence of the capacity factor(k') on the column temperature and enthalpy calculated by van't Hoff plot. From these results, it was confirmed that the retention mechanism of iron(III)porphyrin complexes in reversed-phase liquid chromatography was invariant under the condition of various temperature, and the solvophobic binding process exhibited isoequilibrium behavior.