• Journal of the Korean Chemical Society
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• v.50 no.1
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• pp.46-52
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• 2006

studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p-X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and (p-X)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin.

• Applied Chemistry for Engineering
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• v.3 no.4
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• pp.579-587
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• 1992

It was explored, whether the usual course of the ozonolysis of olefins can be modified with the help of pyridine. In the First step, the ozone oxidation of trans-3-hexene was performed with and without pyridine in the inert solvents n-pentane and dichloromethane. In addition, base catalyzed decompositions of monomeric and polymeric ozonides were also examined to identify the reaction mechanism. The reaction products were identified by modern analytical tools. The results of this work showed that reactions of ozone with olefins in the absence of pyridine in aprotic solvents gave, one hand, dominantly peroxidic products, namely monomeric and polymeric ozonides. The other hand, they in the presence of pyridine gave only the non-peroxidic products, namely propionaldehyde and rearranged propionic acid without peroxidic products. It seems, also, that the pyridine-catalyzed isomerization of the Criegee zwitterion of trans-3-hexene to give propionic acid takes place in the ozone oxidation of trans-3-hexene.

• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.295-301
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• 1994

The Ru(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), and Pd(Ⅱ) complexes of N$_4$-polydentate ligands(meso-Me$_6$-[14]-ane, rac-Me$_6$-[14]-ane, and cyclam) have been prepared and their catalytic activity and selectivity in the oxidation of olefins in the presence of oxidant such as NaOCl, H$_2$O$_2$, t-BuOOH, and PhIO studied. The oxidations of cyclohexene, 1-hexene, cyclooctene, 1-octene, and styrene as substrates have been investigated gas chromatographically. The Ru(Ⅲ)-N$_4$ complexes showed high selectivity for epoxide in the catalyzed oxidation of olefins with NaOCl. The catalytic activities of Ru(Ⅲ)-N$_4$ complexes were discussed in terms of the flexibility of N$_4$-polydentate ligands, the Ru(Ⅲ)-Cl bond interaction and the steric effect of oxidants. The oxidation of 1-octene using PhIO as oxidant was carried out to verify. The Pd(Ⅱ) complex turned out to be more active catalyst than the Ni(Ⅱ) complexes.

• Journal of the Korean Chemical Society
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• v.38 no.4
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• pp.333-335
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• 1994

• Journal of the Korean Chemical Society
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• v.39 no.5
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• pp.364-370
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• 1995

The catalytic oxidations of several olefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin (M=Ga(III), In(III), Tl(III)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were $(p-CH_3O)TPP,\;(p-CH_3)TPP,\;TPP,\;(p-F)TPP,\;(p-Cl)TPP\;and\;(F_20)TPP$ (TPP=tetraphenylporphyrin), and olefins were $(p-CH_3O)-,\;(p-CH_3)-,\;(p-H)-,\;(p-F)-,\;(p-Cl)-\;and\;(p-Br)styrene$styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the ${\sigma}^+$ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(III)- and Tl(III)-porphyrins turned out to be more active catalysts than Ga(III)-porphyrin.

• Applied Chemistry for Engineering
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• v.27 no.2
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• pp.128-134
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• 2016

Due to the great development made in converting the shale gas into the more valuable products, research and commercialization for production technology of olefins like propylene, butenes, butadiene from light alkanes have been intensively investigated. Especially the technology using oxygen like oxidative dehydrogenation or selective hydrogen combustion to overcome thermodynamic limit of direct dehydrogenation conversion has been extensively studied and some cases of applying this technology to the plant scale was reported. In this review, we have categorized the technology into two parts; gas phase oxygen utilization technology and lattice oxygen utilization technology. The trends, results and future direction of the technology are discussed.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.646-656
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• 1994

The ${\omega}$-formyl carboxylic acid was produced by ozone oxidation of cycloolefins in the presence of pyridine and its production yield was examined by varying temperature and solvent. As the reaction temperature increased, the yield of ${\alpha}$, ${\omega}$-dicarboxylic acid increased whereas that of ${\alpha}$, ${\omega}$-dialdehyde decreased. As the polarity of solvent increased, a higher yield of desired ${\omega}$-formyl carboxylic acid was obtained, whereas the yield of unwanted polymeric ozonide decreased. The yields of ${\omega}$-formyl carboxylic acid from ozone oxidation of cyclohexene, cyclooctene and cyclododecene at $0^{\circ}C$ and in methylene chloride solvent were 59.30%, 55.20%, and 36.72%, respectively.

• Applied Chemistry for Engineering
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• v.21 no.5
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• pp.586-589
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• 2010

In present work, oxidative addition reaction of 1,3-cycleohexandion (1,3-CHD) with ethyl vinyl ether (EVE) was attempted utilizing $Ag_2CO_3$/celite (SC) reagent. In order to optimize reaction conditions, we surveyed several solvents for the production of dihydrofuran with the (SC) system. The yield of the acetonitrile (AN), dimethyl sulfoxide (DMSO), benzene (BZ), and heptane (HT) are given 78, 40, 15, and 10%, respectively. Therefore, we studied the solvent effects on yields by using PM3 and ZINDO/1 parameter of semi-empirical method of HyperChem7.0 molecular modeling program.

• Journal of the Korean Applied Science and Technology
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• v.15 no.2
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• pp.41-48
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• 1998

The catalytic oxidations of several cycloolefins in $CH_2Cl_2$ were been investigated using Mn(III)-, Fe(III)-porphyrin complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)TTP,\;(p-CH_3)TTP,$ TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})TPP$ (TPP = tetraphenylporphyrin), and olefins were cyclopentene, cyclohexene and cycloheptene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. The conversion of cycloalkene followed the order of $C_5\;<\;C_6\;<\;C_7$.

• Journal of the Korean Applied Science and Technology
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• v.21 no.1
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• pp.76-88
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• 2004

The catalytic oxidation reaction of several cycloolefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin(M = Ga(III), In(III) and TI(III) complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)$TPP, $(p-CH_3)$TPP, TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})$TPP (TPP=5,10,15,20-tetraphenyl-21H,23H-porphyrin) and olefins were cyclopentene, cyclohexene, cycloheptene and cyclooctene, The substrate conversion yield(%) was investigated according to the radius effect of non-redox metal ion, substituent effect and hindrance effect of metalloporphyrin. The conversion yield of cycloolefin was in the following order : $C_5$ < $C_6$ < $C_7$ = $C_8$.