• Title/Summary/Keyword: epoxidation

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Studies on the Catalytic Effects of Organic Compounds by Polymer-bonded Metalloporphyrins (고분자 결합 Metalloporphyrin을 이용한 유기물질의 산화촉매에 대한 연구)

  • Lee Sung-Ju;Paeng Ki-Jung;Whang Kyu-Ja
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.744-752
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    • 1992
  • Polymer bonded metalloporphyrins are synthesized by reaction between Fe(III) protoporphyrin or Mn(II) tetrakis(4-N-carboxyphenyl)porphyrin with polystyrene divinylbenzene copolymer. The spectroscopic properties of synthetic polymer bonded metalloporphyrins are investigated by using resonance Raman spectrometer. By synthetic polymer bonded metalloporphyrins as catalyst, which are model of cytochrome P-450 and peroxidases, epoxidation of olefins and oxidation of alkanes are achieved with H2O2 as oxidant. The catalytic efficiencies with polymer bonded metalloporphyrins are improved on that with corresponding nonpolymer bonded metalloporphyrins. Especially those can be reused because of stability against oxidant. Electron donating imidazole derivatives, which are attached in 5th position of central metal of metalloporphyrins, enhance the catalytic efficiencies.

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Vinyl Addition Copolymerization of Norbornene/5-Vinyl-2-norbornene with Cationic $\eta^{3_}$-Allyl Palladium Catalyst and Their Post-Reaction (양이온성 $\eta^{3_}$알릴 팔라듐 촉매를 사용한 노보넨/5-비닐-2-노보넨의 비닐 부가 공중합과 이를 이용한 고분자 후반응)

  • 안재철;박수현;이광희;박기홍
    • Polymer(Korea)
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    • v.27 no.5
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    • pp.429-435
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    • 2003
  • Vinyl addition copolymerizations of norbornene (NB) and 5-vinyl-2-norbomene (VNB) were carried out using a cationic η$^3$-allyl palladium catalyst in the various mole ratio of comonomers. The copolymers could be obtained in good yield (65∼85%) with high weight-average molecular weights (M$_{w}$ > 760,000). Depending on increasing VNB contents, the molecular weight and yield of the copolymers decreased. FT-IR analysis confirmed that actual contents of VNB in polymer were proportional to the feeding content of VNB. From $^1$H-NMR spectroscopy, we found that both exo and endo VNB isomer were copolymerized with NB. Thermal stabilities of NB-VNB copolymers were independent on the VNB content and their initial decomposition temperatures were about 300 C. The NB-VNB copolymers were followed by epoxidation by using m-CPBA and hydroxylation by 9-BBN, respectively, and these post-polymers were characterized by FT-IR spectroscopy and $^1$H-NMR analysis..

Biotransformation of Aldrin and Chlorpyrifos-methyl by Anabaena sp. PCC 7120

  • Park, Byeoung-Soo;Lee, Sung-Eun
    • Korean Journal of Environmental Agriculture
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    • v.29 no.2
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    • pp.184-188
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    • 2010
  • A cyanobacteria species, Anabaena sp. PCC 7120, was tested to assess its biotransformation ability on two widely used insecticides, aldrin and chlorpyrifos-methyl, in the culture medium. The blue-green alga metabolized aldrin mainly to dieldrin by an epoxidation reaction with the participation of cytochrome P450-dependent monooxygenase in the cyanobacteria. The blue-green alga also produced chlorpyrifosmethyl oxon as a primary metabolite from chlorpyrifos-methyl via a desulfuration reaction, presumably conducted by cytochrome P450-dependent monooxygenase. Therefore, two insecticides might be possibly dissipated by cytochrome P450-dependent monooxygenases in the blue-green algae in the contaminated environments.

Synthesis and in vitro Cytotoxicity Monoterpenoid as New Antitumor Agents (Monoterpenoid계의 새로운 항암제 합성 및 In vitro 세포독성 평가)

  • 이민정;김대근;백형근;이강노;정규혁
    • Biomolecules & Therapeutics
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    • v.9 no.3
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    • pp.143-155
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    • 2001
  • Many attention has been focused on developing new chemotherapeutic agents for a treatment of cancer from natural products. From Carpesium divaricatum S. et Z. (Compositae), various monoterpenoid compounds were isolated and exhibited mild antitumor activity against human tumor cell lines. These facts prompted us to explore the structure-activity relationship of these compounds. The synthesis of monoterpenoid compound was accomplished by Fries rearrangement, Grignard reaction, elimination, allylic oxidation, esterification and epoxidation as key steps. The results of in vitro cytotoxicity (A549, SK-OV-3, SK-MEL-2, XF498, HCT15) of the synthesised compounds are as follows: First of all, epoxide moiety is prerequisite for cytotoxic activity in diester compound. Any kind of compounds with olefin or diol moiety instead of epoxide ring exhibited poor or mild cytotoxic activity respectively. Of o-acetoxy and isobutoxy epoxy esters, p-sub-stituted phenylacetate compounds exhibited high cytotoxic activities against SK-MEL-2 and HCT15.

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Epoxyalkanoyls as Novel ACE Inhibitors

  • P. Choo, Hea-Young;Yoon, Hea-Ran;Park, Hwha-Soon;Kim, Dong-Hyun;Park, Jong-Sei;Kim, Dong-H.
    • Archives of Pharmacal Research
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    • v.21 no.2
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    • pp.168-173
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    • 1998
  • The epoxyalkanoyl derivatives were designed and synthesized as ACE inhibitors. Coupling of unsaturated carboxylic acids with amino acids and following epoxidation with dimethyldioxirane gave the epoxyalkanoyls with high yield. The inhibitory activity of synthesized compounds on angiotensin converting enzyme was $IC_{50}$ values of 0.06~5.5 ${\mu}M$.

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An Approach to the Enantioselective Synthesis of the Crucial Intermediate of Conformationally Locked Nucleosides (형태학적으로 고정된 뉴클레오사이드 주요중간체의 Enantioselective 합성법 탐색)

  • Kim, Soon-Ai;Kim, Hak-Sung
    • YAKHAK HOEJI
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    • v.54 no.6
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    • pp.474-480
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    • 2010
  • Conformationally locked nucleosides are important in searching selective agonists and antagonists for P2Y receptors. There were two previous synthetic works of the crucial intermediate, cyclopentenyl alcohol (3), which had some inefficiency like using too strong dianionic base and synthesis of racemate. Here we describes a facile synthesis of the intermediate using Sharpless epoxidation and the opening of epoxide ring using zinc, followed by Grubb's metathesis as key steps. The intermediate was converted to the southern bicyclo[3.2.0]heptane for confirming its usefulness.

Synthesis of Epoxidized Soybean Oil (ESO) and its Blends with Tetrafunctional Epoxy Resins (Epoxidized soybean oil(ESO)의 합성 및 4 관능성 에폭시 수지/ESO 블렌드 시스템의 물성)

  • Lee, Jae-Rock;Jin, Fan-Long;Park, Soo-Jin
    • Proceedings of the Korean Society For Composite Materials Conference
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    • 2003.04a
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    • pp.180-183
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    • 2003
  • In this work. a potential inexpensive epoxy resin. epoxidized soybean oil (ESO) was synthesized and applied as a toughening agent for 4.4'-tetradiglycidyl diaminodiphenyl methane (TGDDM). The chemical structure of ESO was characterized by FT-IR, $^1H NMR, and ^{13}C NMR$ spectroscopy. The curing behaviors. thermal stabilities. fracture toughness. and flexural strength of TGDDM/ESO blend systems were investigated by using the dynamic DSC. thermogravimetric analysis (TGA). and flexural tests. The thermal stabilities of TGDDM/ESO blend systems were decreased with increasing ESO contents. whereas the critical stress intensity factor ($K_{IC}$) and flexural strength ($\sigma_f$) were increased with ESO contents up to 10 wt% ESO.

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Autoxidation of Cycloalkenes by the System “Molecular Oxygen-bis(acetylacetonato) Cobalt (II) Complex-butyraldehyde”

  • Fang, Zhao;Tang, Rui-Ren;Zhang, Rui-Rong;Huang, Ke-long
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2208-2212
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    • 2009
  • Oxidation of cycloalkenes with $O_2$ promoted by heterogeneous bis(acetylacetonato) cobalt (II) complex catalyst which can be recycled has been performed under mild conditions. It was found that $\beta$-ionone, cyclohexene, 1-methylcyclohexene, and $\alpha$-ionone were efficiently oxidized with $O_2$ in the presence of Co (II) complex and butyraldehyde at $55\;{^{\circ}C}$. A simple treatment of the resulting products led to epoxides as predominant products and a small amounts of allylic oxides, the chemoselectivity for the former being 82.1 - 90.8% with a 70.6 - 98.6% substrate conversion. On the other hand, oxidation of 1-phenylcyclohexene, 1-cyclohex-1-enylethan-1-one, $\alpha$-pinene, and $\beta$-pinene gave allylic oxides as major products.

Synthesis, End-Functionalization and Characterization of Hyperbranched Polysiloxysilanes from $AB_3$ Type Monomer

  • Ishida, Yoshihito;Yokomachi, Kazutoshi;Seino, Makoto;Hayakawa, Teruaki;Kakimoto, Masa-aki
    • Macromolecular Research
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    • v.15 no.2
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    • pp.147-153
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    • 2007
  • Hyperbranched polysiloxysilanes (HBPSs), with a variety of terminal functional groups (vinyl, epoxy, carboxyl and hydroxyl), were synthesized by the self-polymerization of an $AB_3$ type monomer of tris(dimethylvinylsiloxy) silane, with subsequent end-functionalizations, such as epoxidation and radical addition reaction, respectively. The ratio of the $\alpha-and$ $\beta-addition$ linkages in the HBPS polymerized by hydrosilylation of the $AB_3$ monomer was found to be approximately 1 to 3. The thermal stability and solubility were affected by the terminal functional groups.

Concise Synthesis of (±)-Rhinacanthin A, Dehydro α-Lapachone, and β-Lapachone, and Pyranonaphthoquinone Derivatives

  • Wang, Xue;Chen, Ye;Lee, Yong-Rok
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.153-156
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    • 2011
  • A concise synthesis of (${\pm}$)-rhinacanthin A is achieved in two steps by epoxidation of dehydro-$\alpha$-lapachone, followed by chemo- and regioselective reduction. Dehydro-$\alpha$-lapachone was also synthesized in two steps starting from 4-methoxy-1-naphthol by ethylenediamine diaetate (EDDA)-catalyzed benzopyran formation and a CAN-mediated oxidation reaction. $\beta$-Lapachone was synthesized in three steps from 4-methoxy-1-naphthol by benzopyran formation, catalytic hydrogenation, and Jones oxidation. As additional reactions, synthesis of pyranonaphthoquinone derivatives with the pyranokunthone B skeleton has been achieved in a single step from readily available 2-hydroxy-6-methoxy-1,4-naphthoquinone and 2-hydroxy-7-methoxy-1,4-naphthoquinone.