• Title/Summary/Keyword: PPh3

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Evaluation of L-FMUS as a potent anti-HBV agent

  • Woo, Seong-Ju;Lee, Hae-Sung;Cheong, Min-Young;Ahn, Kwang-Hyun;Park, Ki-Seok;Koo, Chang-Hui
    • Proceedings of the PSK Conference
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    • 2003.04a
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    • pp.242.1-242.1
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    • 2003
  • The nucleoside analogue, L-FMUS was synthesized from L-FMAU which has been shown to have significant antiviral activity against hepatitis B virus (HBV). It was prepared by two steps. First, 5'hydroxyl of L-FMAU was substituted by thioacetyl group using diisopropylazodicarboxylate(DIAD), Triphenyl phosphine(PPh3) and thioacetic acid in anhydrous THF. (omitted)

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Effects of Catalysts and Blowing Agents on the Physical Properties and Cell Morphology of Polyurethane Foams (폴리우레탄 폼의 물성과 Cell Morphology에 대한 촉매와 발포제의 영향)

  • Kwon, Hyun;Lee, Su Heon;Kim, Sang Bum;Bang, Moon-Soo;Kim, Youn Cheol
    • Applied Chemistry for Engineering
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    • v.16 no.3
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    • pp.379-384
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    • 2005
  • Polyurethane foams (PUFs) were prepared from polymeric 4,4'-diphenylmethane diisocyanate (PMDI), seven polyols with different functionalities and OH values, silicone surfactant, two catalysts, and three blowing agents. Chlorofluorocarbon (CFC-11), hydrochlorofluorocarbon (HCFC-141b) and hydrofluorocarbon (HFC-365mfc) were used as blowing agents. The effect of gelling and blowing catalysts on basic properties and cell structure of PUF with HCFC-141b was investigated. The cell size of the PUF decreased with an increase in the amount of catalyst from 0 to 2 pph (parts per hundred polyol). In the case of gelling type catalyst, the compressive strength increased from 11.9 to $12.66kg_f/cm^2$ with an increase in the amount catalyst from 0 to 2 pph but the density did not change significantly. The gelling time, density, and compressive strength of the PUF with three different blowing agents were measured. There was no detectable change in their properties. However, the cell structure of PUF with HCFC-141b was not uniform as in the other systems.

Synthesis and Characterization of Polyamides and Polyester Prepareds by Palladium-catalyzed CO Insertion Reaction (고강도 엔지니어링 플라스틱재료의 합성 - I. Palladium-catalyzed CO Insertion 반응에 의한 전방향족 Polyamides와 Polyester의 합성 -)

  • Jun, Chang Lim;Park, Sang Bok;Park, Nae Joung;Yum, Sung Bai
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.694-700
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    • 1992
  • Aromatic polyamides and polyesters with fexible spacers are prepared by Heck reaction with palladium catalysts In presence of carbon monoxide gas. Dichlorobis(triphenyl phosphine) plladium(II) ($PdCl_2(PPh_3)_2$) and palladium chloride ($PbCl_2$) are used as catalysts. Polyamides and polyesters prepared by his polymerization system have similar transition temperatures. Flexible spacer substituted on phenylene units are varied from hexyl to hexadecyl, the length of spacers effected on transition temperatures of substituted polymers.

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Kinetics and Mechanism of Substitution Reaction of $PPN^+(\eta^n-MeCp)Mn(CO)_2\;Cl^-$ with $PR_3$(R=Me, Et, OEt, $C_6H_5$)

  • Park, Yong Gwang;Lee, Yong Gu;Kim, Gyu Sik
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.138-142
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    • 1996
  • The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

Facile Synthesis of Natural Moracin Compounds using Pd(OAc)2/P(tBu)3-HBF4 as a Sonogashira Coupling Reagent

  • Lee, Jae Jun;Yun, So-Ra;Jun, Jong-Gab
    • Bulletin of the Korean Chemical Society
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    • v.35 no.12
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    • pp.3453-3458
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    • 2014
  • An efficient and practical synthesis of natural moracins, which have diverse range of biological properties including anticancer, antioxidant, and antibacterial activities, has been achieved using $Pd(OAc)_2/P(^tBu)_3-HBF_4$ as a Sonogashira coupling reagent which solved the unreactive problems in case of higher electron density of haloaryl compounds in the reaction. Lowering electron density of halophenol with acetylation and changing Sonogashira coupling reagent from $PdCl_2(PPh_3)_2$ to $Pd(OAc)_2/P(^tBu)_3-HBF_4$ smoothly produce the benzofuran structures in the syntheses of moracins M, N and S. The electron deficient halobenzaldehyde, however, easily forms the benzofuran using original Sonogashira conditions, and utilized for the first synthesis of moracin Y.

Synthesis, Spectroscopic Studies of Binuclear Ruthenium(II) Carbonyl Thiosemicarba-zone Complexes Containing PPh3/AsPh3 as Co-ligands: DNA Binding/Cleavage

  • Sampath, K.;Sathiyaraj, S.;Jayabalakrishnan, C.
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.367-373
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    • 2013
  • The ruthenium(II) ferrocenyl heterocyclic thiosemicarbazone complexes of the type $[RuCl(CO)(EPh_3)]_2L$ (where E = P/As; L = binucleating monobasic tridendate thiosemicarbazone ligand) have been investigated. Strutural features were determined by analytical and spectral techniques. Binding of these complexes with CT-DNA by absorption spectral study indicates that the ruthenium(II) complexes form adducts with DNA and has intrinsic binding constant in the range of $3.3{\times}10^4-1.2{\times}10^5M^{-1}$. The complexes exhibit a remarkable DNA cleavage activity with CT-DNA in the presence of hydrogen oxide and the cleavage activity depends on dosage.

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.

The Oxidation of Hydrazobenzene Catalyzed by Cobalt Complexes in Nonaqueous Solvents

  • Kim, Stephen S.B.;Hommer, Roger B.;Cannon, Roderick D.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.2
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    • pp.255-265
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    • 2006
  • The oxidation of hydrazobenzene by molecular oxygen in the polar solvent methanol is catalysed by a Schiff's base complex Co(3MeOsalen) which is a synthetic oxygen carrier. The products are trans-azobenzene and water. The rate of the reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a ternary complex of catalyst, hydrazobenzene and molecular oxygen has been proposed. The kinetic studies show that a ternary complex $CoL{\cdot}H_2AB{\cdot}O_2$ is involved in the rate determining step. The reactions are summarised in a catalytic cycle. The kinetic data suggest that a ternary complex involving Co(3MeOsalen), triphenyl-phosphine and molecular oxygen is catalytically acive species but at higher triphenylphosphine concentrations the catalyst becomes inactive. The destruction of the catalytic activity could be due to the catalyst becoming coordinated with triphenyl phosphine at both z axis sites of the complex e.g. Co (3MeOsalen)$(PPh_3)_2$.

The Comparative Study in the Oxygen Atom Transfer Reaction by Ruthenium Mono-Oxo Complexes

  • Seok, Won K.;Son, Yung J.;Moon, Sung W.;Lee, Heung N.
    • 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.

Palladium Catalyzed Carbonylative Vinylation of Aryl Halides with Olefins and Carbon Monoxide

  • Kim, Jin-Il;Ryu, Cheol-Mo
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.246-250
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    • 1987
  • The reaction of aryl iodides or bromides with olefins in the presence of 1 mol % of $PdCl_2(PPh_3)_2$ and 3 equiv. of $n-Bu_3N\; at\; 100^{\circ}C$ in carbon monoxide atmosphere gave the corresponding aryl vinyl ketones in good yields with small amount of vinylated 1-aryl olefins. But, when the reaction was proceeded under the 10 atm of carbon monoxide, aryl vinyl ${\alpha}$-diketones and aryl vinyl ketones were obtained in moderate to good yields. The reaction was tolerant of a wide variety of functional groups on either the aryl halides or olefin compounds. Reactivity of aryl halide decrease in the order; aryl iodide > aryl bromide ${\gg}$aryl chloride. In general, the reaction proceeded well and gave good yields of aryl vinyl ketones and aryl vinyl ${\alpha}$-diketones when reactants are substituted with electron withdrawing groups.