• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1195-1199
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• 1999

2-(2,4,5-Trimethoxyphenyl)-4-methylene-1,3-dioxolane (1b), 2-(2,4,6-trimethoxyphenyl)-4-methylene-1,3-di-oxolane (2b), and 2-(3,4,5-trimethoxyphenyl)-4-methylene-1,3-dioxolane (3b) were prepared and polymerized with boron trifluoride. Boron trifluoride catalyzed reaction proceeded via mainly ring-opening polymerization and cyclization reaction to yield poly(keto ether) and 3(2H)-dihydrofuranone. The yields of polymer and cyclized product exhibited a dependency on the position of the methoxy substituents in the benzene ring of 2-phenyl-4-methylene-1,3-dioxolane derivatives. Electrophilic attack of methylene or oxygen atom on 4-meth-ylene-1,3-dioxolane ring were suggested for the polymerization and cyclization.

• Bulletin of the Korean Chemical Society
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• v.20 no.6
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• pp.643-647
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• 1999

Hydropalladium carboxylates, formed from π-allylpalladium chloride dimer plus carboxylic acids, have been shown to catalyze cyclization of structurally diverse enediynes to form the corresponding six- or five-membered rings depending upon the reaction conditions. Some enediynes having an Oxygen linker in an appropriate position under the similar condition yielded the corresponding cyclopropanation products in highly stereoselective manner. A study using deuterated formic acid has proven that the alkylpalladium intermediates formed in our conditions were reduced by the pendant formate ligand. The dienediyne 10 yielded only the tricyclic product 12 in 67% yield, although it was expected to frrm the cyclic product 11. All these cyclizations seemed to occur via the corresponding alkylpalladium intermediates I. which could proceed to the corresponding cyclic products depending on the reaction conditions and the substrates. The study using ceuterated formic acid could provide an important information to understand the present cyclization mechanism. Overall the present study could play an important role in developing new synthetic methodologies for constructing complex polycyclic compounds.

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.194-200
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• 1990

Various mechanistic aspects of the A2 hydrolysis of methyl acetimidate were explored using the MNDO method. As in thecorresponding reactions of acetamide and methyl carbamate, a proton transfer pre-equilibrium exists between the N-protonated and the O-protonated tautomers, and the subsequent hydrolysis proceeds from the more stable N-protonated form. Of the two reaction pathways, the $A_{AL}2$ path is favored in the gas phase and in concentrated acid solutions, whereas the $A_{AC}2$ path is favored in less acidic solutions with a stable cationic tetrahedral intermediate formed in the rate determining step. Negative charge development on the alkoxy oxygen in the transition state suggested a rate increase with the increase in the electron withdrawing power of the alkoxy group. Calculations on the reaction processes with AM1 indicated that MNDO is more reliable in this type of work, although AM1 is better than MNDO in reproducing hydrogen bonds.

• Bulletin of the Korean Chemical Society
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• v.6 no.5
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• pp.291-295
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• 1985

The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

• Bulletin of the Korean Chemical Society
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• v.22 no.3
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• pp.303-307
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• 2001

The ignition of propane was investigated behind reflected shock waves in the temperature range of 1350-1800 K and the pressure range of 0.75-1.57 bar. The ignition delay time was measured from the increase of pressure and OH emission in the C3H8-O2-Ar system. The relationship between the ignition delay time and the concentrations of propane and oxygen was determined in the form of mass-action expression with an Arrhenius temperature dependence. The numerical calculations were also performed to elucidate the important steps in the reaction scheme of propane ignition using various reaction mechanisms. The ignition delay times calculated from the mechanism of Sung et al.1 were in good agreement with the observed ones.

• Applied Chemistry for Engineering
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• v.9 no.3
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• pp.355-360
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• 1998

Reduction activity of precious metal-loaded HZSM-5 for NO has been studied and was compared to that of Cu-HZSM-5 in the presence of excess oxygen. It was found that among the catalysts used in this study, Ru-HZSM-5 was the most active catalyst for the reduction of NO to $N_2$ in the absence of hydrocarbon reductant. The highest conversion obtained was 45%. No severe inhibition of water vapor to the reduction was observed. It is suggested that the higher catalytic activity of Ru-HZSM-5 may result from the better ability to oxidize NO to $NO_2$ in the presence of excess oxygen. A proposed reaction mechanism for the reduction of NO to $N_2$ in the presence of excess oxygen is that NO is oxidized to $NO_2$ on the surface of Ru-HZSM-5 catalyst and the adsorbed $NO_2$ on the surface is then decomposed to $N_2$. $NO_2$ is supposed to the reaction.

• Korean Journal of Food Science and Technology
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• v.31 no.2
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• pp.527-534
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• 1999

This study was carried out to investigate the effects of pine needle extracts on lipid oxidation and free radical reaction in iron sources reacted with active oxygen species. The results were summarized as follow; the catalytic effects of active oxygen on lipid oxidation in oil emulsion tended to be showed $OH,\;H_2O_2\;and\;KO_2$ in order. At the same time, pine needle extracts itself were tended to be showed a little catalytic effects. Active oxygen scavenging ability of pine needle extracts didn't show, but pine needle extracts played role as a strong chelating agents to bind iron ion if $Fe^{2+}$ ion exist in oil emulsion. The content of $Fe^{2+}$ ion and total iron in CPNP were higher than those of HPNP and FPN. The content of ascorbic acid of FPN showed the highest (87.77 ppm) among several pine needle extracts. Electron donating ability of HPNP and CPNP were 81% and 78%, respectively, which were showed higher content than those of FPN. The SOD-like activity of HPNP showed 44.30%, compared to other pine needle extracts which means the most strong antioxidant reaction. The nitrite scavenging effects were tended to be different, depending on pH value as pH value was increased. Especially, they didn't show the nitrite scavenging effect in pH6.0.

• Journal of the Korean Chemical Society
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• v.48 no.1
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• pp.99-102
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• 2004

• Maxillofacial Plastic and Reconstructive Surgery
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• v.18 no.3
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• pp.448-453
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• 1996

This is case report of florid osseous dysplasia occurred in the entire maxilla and mandible of 47-year-old female. Florid osseous dysplasia is an expansile, exuberant asymptomatic form of benign fibro-osseous disease of the periodontal ligament, often associated with jaw cysts and to be though as an abnormal reaction of bone to irritation or stimulation. The treatment was performed with removal of the necrotic bone, bone curretage and hyperbaric oxygen therapy. The patient did not well postoperatively and has shown sign of persistant infection with pus discharge.