• Title/Summary/Keyword: Chemical coupling

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Synthesis of 3,4,5-Trisubstituted Isoxazoles through Gold-Catalyzed Cascade Cyclization-Oxidative Alkynylation and Cyclization-Fluorination of 2-Alkynone O-Methyloximes

  • Song, Doo-Hee;Ryu, Jae-Sang
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2635-2644
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    • 2014
  • Gold-catalyzed tandem cyclization-oxidative alkynylation and cyclization-fluorination reactions of 2-alkynone O-methyloximes are described. The reactions proceed smoothly at room temperature in the presence of 10 mol % of $(PPh_3)AuNTf_2$, 2.5 equivalents of selectfluor, and 2 equivalents of $K_3PO_4$. 2-Alkynone O-methyloximes undergo intramolecular oxyauration/cyclization and ensuing oxidative cross-coupling and fluorination process to afford the corresponding 3,4,5-trisubstituted isoxazoles in a cascade manner.

Synthesis of Phosphates and Phosphoric Amides (Ⅰ) (Phosphates 및 Phosphoric Amides의 합성 (제1보))

  • Kil-Yeong Choi;Sam-Kwon Choi
    • Journal of the Korean Chemical Society
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    • v.24 no.6
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    • pp.457-462
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    • 1980
  • Phosphates and phosphoric amides were synthesized by the reaction of phosphoryl chloride with allyl alcohol, 2,3-dibromopropanol, 2-pyrrolidone and ethylenimine. All of these compounds were thermally very unstable. Allyl phosphorodichoridate and diallyl phosphorochloridate gave significant amount of polymeric products when they were distilled. IR spectra showed characteristic P=O stretching bands between 1300 and $1200 cm^{-1}$ and NMR spectra were very complicated due to the long range coupling effect of phosphorus atom. And mass spectrum of 2,3-dibromopropyl phosphorodichloridate gave no indication of molecular ion peak.

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Studies on the Characteristics of Humic Acid and its Utilizations (Part 4). Manufacturing of Azo-dyes from Humic Acid (土炭흄酸의 性狀 및 應用에 關한 硏究 (第4報) 아조染料 製造에 관하여)

  • Han Kyoungsuk;Kim, Won Taek
    • Journal of the Korean Chemical Society
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    • v.16 no.5
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    • pp.320-327
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    • 1972
  • The coupling of aromatic diazonium salts with humic or nitrohumic acid, as a supplemental method of determining the structure and utilization of humic acid, were studied. The following results were obtained. 1) Humic acids have many vacan to-and p-positions in their phenol kernels. 2) Humic acids have not so many benzene kernels in their structure units. 3) When coupled with aromatic diazonium salts (such as aniline, aminonaphthalene and aminoanthraquinone derivatives), various azo-dye were obtained.

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Expeditious Synthesis of Natural Benzofuran, Eupomatenoid-6 by Umpolung of α-Aminophosphonates

  • Damodar, Kongara;Jun, Jong-Gab
    • Bulletin of the Korean Chemical Society
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    • v.35 no.12
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    • pp.3618-3622
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    • 2014
  • Simple and practical synthesis of natural benzofuran derivative eupomatenoid-6 via Horner-Emmons type condensation as the key step is described. The umpolung property of aldehyde derivative, ${\alpha}$-aminophosphonate was efficiently employed in this reaction. ${\alpha}$-Aminophosphonate of anisaldehyde subjected to Horner-Emmons type condensation with 5-bromo-2-methoxybenzaldehyde to yield the deoxybenzoin, which was further methylated and then underwent tandem demethylation-cyclodehydration to afford the benzofuran scaffold in excellent yield. Finally Suzuki coupling with propenyl boronic acid afforded eupomatenoid-6 with an overall yield of 56.8%.

Dehydropolycondensation of Aminophenols under the Catalytic Acition of Metallic Chelate Compounds (Ⅲ) Reactions of the Isomers, Reaction Mechanisms, and the Structures of the Oligomers (金屬킬레이트 化合物의 觸媒作用에 依한 Aminophenol 類의 酸化的 重縮合反應 (Ⅲ) 異性體의 反應, 反應機構 및 生成物의 構造)

  • Choi, Kyu-Suck
    • Journal of the Korean Chemical Society
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    • v.12 no.3
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    • pp.128-137
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    • 1968
  • In the oligomerization of p-aminophenol by the catalytic action of Fe-EDTA complex in the aqueous medium, the mixed complex intermediate, Fe-EDTA-M type, is considered to be formed, from which active radicals of the monomer are produced. In this system, polymerization is presumed to proceed as follows: Free radical formation ${\to}$ Coupling ${\to}$ Activation ${\to}$ Coupling, and so on. In this study, the form of the monomer and coordination state in the mixed complex, the catalytic action of Fe-EDTA the complex, the reaction mechanism, and the structure of the oligomers are discussed.

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Spin-Rotation Interaction in Polyatomic Molecules in the Presence of Internal Rotation (內部廻轉存在時의 多原子分子에서의 스핀-廻轉相互作用)

  • Lee Jo W.
    • Journal of the Korean Chemical Society
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    • v.20 no.5
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    • pp.364-373
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    • 1976
  • A magnetic nucleus located on an internal rotor in a polyatomic molecule can interact with the magnetic fields arising from internal rotation as well as end-over-end molecular rotation. In this paper the spin-rotation coupling Hamiltonian for a nuclear spin on a symmetrical internal rotor in a polyatomic molecule is derived. The derived spin-rotation Hamiltonian turns out to be composed of the two parts: the spin-over-all-rotation interaction and the spin-internal-rotation interaction. The relation between the spin-rotation coupling tensor and the magnetic shielding effect is also investigated.

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Investigation of the Binding Affinity between Styrylquinoline Inhibitors and HIV Integrase Using Calculated Nuclear Quadrupole Coupling Constant (NQCC) Parameters (A Theoretical ab initio Study)

  • Rafiee, Marjan A.;Partoee, Tayyebe
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.208-212
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    • 2011
  • In this work, the calculated nuclear quadrupole coupling constants of $^{17}O$ in some styrylquinoline conformers were presented. The calculations were carried out to find the relationships between the charge distribution of styrylquinolines and their pharmaceutical behavior and to explore the differences among the electronic structures of some conformers of these potent HIV IN inhibitors. Furthermore, the HIV IN inhibitory of R1 and R2 rotamers was compared. On the basis of our results: - Charge density on oxygen atoms of carboxyl moiety has a dominant role in the drug activity. - The a conformer in which a divalent hydrogen atom is a link, has more capability in antiviral drug treatment. - The R1 conformer, as a $Mg^{+2}$ chelating agent, is better than R2 conformer and thus it is more inhibitor of HIV IN.

A Quantitative Analysis of $\pi$-Nobonded and Through-Bond Interactions in n-Butane, n-Buthyl Radical and Tetramethylene Diradical$^1$

  • Lee Ikchoon;Cheun Young Gu
    • Bulletin of the Korean Chemical Society
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    • v.3 no.1
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    • pp.1-4
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    • 1982
  • A quantitative treatment of ${\pi}$-nonbonded and $n-{\sigma}^{\ast}$ interactions and through-bond coupling effect was attempted using n-butane, n-butyl radical, and tetramethylene diradical. Results of STO-3G level calculations showed that: (1) conformational preferences can be predicted quantitatively based solely on the additive effect of ${\pi}$-nonbonded and $n-{\sigma}^{\ast}$ interactions, the predominant effect being the ${\pi}$-nonbonded interactions, (2) $(n-{\sigma}^{\ast})_{anti}$ is destabilizing whereas $(n-{\sigma}^{\ast})_{syn}$ is weakly stabilizing, which are contrary to what we expect from the normal $n-{\sigma}^{\ast}$ interaction, (3) througb-bond coupling of the two radical lobes is destabilizing for the triplet but stabilizing for the singlet tetramethylene diradical.

The Effect of Vibrationally Excited Levels on the Pressure Saturation of the Collisional Quenching of the $^3B_1\;State\;of\;SO_2

  • Bae, S. C.
    • Bulletin of the Korean Chemical Society
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    • v.17 no.1
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    • pp.56-60
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    • 1996
  • The pressure saturation effect on the phosphorescence decay rates of the $^3B_1$ State of $SO_2$ has been reinvestigated by the laser induced phosphorescence method in pure $SO_2$. We have attempted to fit the pressure dependence of the phosphorescence decay rates using the radiationless transition model by introducing different coupling constants for each vibrational level ofthe 3B1 state. The experimental decay rates can be fitted well, when the coupling constants for the (0,0,0), (0,1,0) and (0,2,0) levels of the $^3B_1$ state are $7.2\;{\times}\;10^{-4}$, $2.2\;{\times}\;10^{-3}$ and $5.9\;{\times}\;10^{-3}\;cm^{-1}$, respectively.