• Title/Summary/Keyword: Chemical reactions

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Indium and Gallium-Mediated Addition Reactions

  • Lee, Phil-Ho
    • Bulletin of the Korean Chemical Society
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    • v.28 no.1
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    • pp.17-28
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    • 2007
  • Indium and gallium have emerged as useful metals in organic synthesis as a result of its intriguing chemical properties of reactivity, selectivity, and low toxicity. Although indium belongs to a main metal in group 13, its first ionization potential energy is very low and stable in H2O and O2. Therefore, indium-mediated organic reactions are of our current interest. On the basis of these properties of indium, many efficient indium-mediated organic reactions have been recently developed, such as the addition reactions of allylindium to carbonyl and iminium groups, the indium-mediated synthesis of 2-(2-hydroxyethyl)homoallenylsilanes, the indiummediated allylation of keto esters with allyl halides, sonochemical Reformatsky reaction using indium, the indium-mediated selective introduction of allenyl and propargyl groups at C-4 position of 2-azetidinones, the indium-mediated Michael addition and Hosomi-Sakurai reactions, the indium-mediated β-allylation, β- propargylation and β-allenylation onto α,β-unsaturated ketones, the highly efficient 1,4-addition of 1,3-diesters to conjugated enones by indium and TMSCl, and the intramolecular carboindation reactions. Also, we found gallium-mediated organic reactions such as addition reactions of propargylgallium to carbonyl group and regioselective allylgallation of terminal alkynes.

Prediction of a Strong Effect of a Wek Magnetic Field on Diffusion Assisted Reactions in Non Equilibrium Conditions

  • Kipriyanov, Alexey A. Jr.;Purtov, Peter A.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.1009-1014
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    • 2012
  • The influence of magnetic fields on chemical processes has long been the subject of interest to researchers. For this time numerous investigations show that commonly the effect of a magnetic field on chemical reactions is insignificant with impact less than 10 percent. However, there are some papers that point to the observation of external magnetic field effect on chemical and biochemical systems actually having a significant impact on the reactions. Thus, of great interest is an active search for rather simple but realistic models, that are based on physically explicit assumptions and able to account for a strong effect of low magnetic fields. The present work theoretically deals with two models explaining how an applied weak magnetic field might influence the steady state of a non-equilibrium chemical system. It is assumed that external magnetic field can have effect on the rates of radical reactions occurring in a system. This, in turn, leads to bifurcation of the nonequilibrium stationary state and, thus, to a drastic change in the properties of chemical systems (temperature and reagent concentration).

Synchrotron Radiation Induced Photochemical Reactions for Semiconductor Processes

  • Rhee, Shi-Woo
    • Journal of the Korean Vacuum Society
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    • v.3 no.2
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    • pp.147-157
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    • 1994
  • Valence or core electron excitations induced by Synchrotron radiation (SR) irradiation and ensuing chemical reactions can be applied for semiconductor processes i, e, deposition etching and modifications of thin film materials. Unique selectivity can be achieved by this photochemical reactions in deposition and etching. Some materials can be ecvaporated by SR irradiation which can be utilized for low temperature surface cleaning of thin films. Also SR irradiation significantly lowers the reaction temperature and photon activated surface reactions can be utilized for direct writing or projection lithography of electronic materials. This technique is especially effective in making nanoscale feature size with abrupt and well defined interfaces for next generation electronic devices.

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Reactions of Thioxanthylium Ion with Organomercurials

  • Shin, Dong-Myung;Kim, Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.2 no.3
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    • pp.114-121
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    • 1981
  • Reactions of thioxanthylium ion with dimethyl-, dibenzyl-, diisopropyl-, and diphenylmercury in the air gave 9,9'-methylenedithioxanthene, 9-benzylthioxanthene, 9-acetonylthioxanthene, and 9-phenylthioxanthene, respectively, as a 9-substituted thioxanthene. In contrast with reactions with aromatics with an electron-donating group, large amount of thioxanthene and thioxanthone were obtained. However, only trace amounts of thioxanthene and thioxanthone were obtained from the reaction with dibenzylmercury under nitrogen atmosphere. In order to explain these reactions, one electron transfer between thioxanthylium ion and organomercurials was proposed.

Reactions in Surfactant Solutions(V): Dephosphorylation of p-Nitrophenyldiphenylphosphinate by Benzimidazole Catalyzed with Ethyltri-n-octylammonium Bromide

  • 홍영석;이정근;김현묵
    • Bulletin of the Korean Chemical Society
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    • v.18 no.12
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    • pp.1260-1264
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    • 1997
  • The phase-transfer reagent (PTC), ethyl tri-n-octylammonium bromide (ETABr), strongly catalyzes the reaction of p-nitrophenyldiphenylphosphinate (p-NPDPIN) with benzimidazole (BI) and its anion (BI-). In ETABr solutions, the dephosphorylation reactions exhibit higer than first order kinetics with respect to the nucleophile, BI, and ETABr, suggesting that reactions are occuring in small aggregates of the three species including the substrate, whereas the reaction of p-NPDPIN with OH- is not catalyzed by ETABr. This behavior for the drastic rate-enhancement of the dephosphorylation is refered as 'aggregation complex model' for reactions of hydrophobic organic phosphinates with benzimidazole in hydrophobic quarternary ammonium salt solutions.

New and General Methods for the Synthesis of Arylmethylene Bis(3-Hydroxy-2-Cyclohexene-1-Ones) and Xanthenediones by EDDA and In(OTf)3-Catalyzed One-Pot Domino Knoevenagel/Michael or Koevenagel/Michael/Cyclodehydration Reactions

  • Jung, Doo-Hwan;Lee, Yong-Rok;Kim, Sung-Hong;Lyoo, Won-Seok
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1989-1995
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    • 2009
  • Efficient one-pot synthesis of arylmethylene bis(3-hydroxy-2-cyclohexene-1-ones) and xanthenediones by EDDA and In($OTf)_3$-catalyzed reactions was developed starting from dimedone and aryl aldehydes. The key strategies of these reactions involve domino Knoevenagel/Michael reaction or Koevenagel/Michael/Cyclodehydration reactions. The scope and limitation of the two catalysts under various reaction conditions were investigated and described.

Evaluation of a Radical Mechanistic Probe for NADH-dependent Horse Liver Alcohol Dehydrogenase Reactions by Computer Graphics Modeling

  • Chung Sung Kee;Chodosh Daniel F.
    • Bulletin of the Korean Chemical Society
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    • v.9 no.1
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    • pp.44-48
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    • 1988
  • The feasibility of the reduction of nortricyclanone (1) as a chemical probe for testing the proposed radical mechanism for NAD-dependent horse liver alcohol dehydrogenase (HLADH) reactions has been examined using computer graphics modeling. The resutls of this study suggest that the radical ring-opening of this probe molecule may involve too substantial a geometry reorganization for the molecule to serve as a chemical probe in detecting the possible presence of the radical intermediates in the HLADH reactions. This result suggests that one should exercise caution in extrapolating results obtained from chemically based radical probes in the solution phase to the topologically constrained systems such as enzyme-substrate reactions.

Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

  • Zhang, Xing-Hui;Wang, Ke-Tai;Niu, Teng;Li, Shan-Shan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1403-1408
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    • 2014
  • The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity.