• 제목/요약/키워드: epoxidation

검색결과 103건 처리시간 0.028초

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

  • 이승주;팽기정;황규자
    • 대한화학회지
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    • 제36권5호
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    • pp.744-752
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    • 1992
  • 철(III) protoporphyrin과 망간(II) tetrakis(4-N-carboxyphenyl) Porphyrin을 polystyrene divinylbenzene 공중합체 수지와 반응시켜 고분자결합 금속포피린을 합성하였다. 고분자와 결합된 포피린은 공명라만분광기를 이용, 합성과정에서 포피린과 중심금속의 산화상태 등 여러가지 화학적 성질이 변화되지 않았음으로 확인하였다. 합성된 고분자결합 금속포피린은 싸이토크롬 P-450과 같은 산화촉매효소의 모형화합물로서 과산화수소에 의한 olefin의 epoxidation과 alkane의 oxidation의 촉매로서 사용이 가능하였다. 그 효율은 고분자와 결합하지 않은 동종의 포피린에 비하여 현저히 증가되었으며, 특히 포피린이 산화제에 의해 분해되지 않아 재사용이 가능하였다. 실제 효소에서와 같이 imidazole 유도체와 같은 전자주게 배위자가 포피린 중심금속에 배위한 경우 촉매효과가 더욱 향상되었다.

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

  • 안재철;박수현;이광희;박기홍
    • 폴리머
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    • 제27권5호
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    • pp.429-435
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    • 2003
  • 양이온η$^3$-알릴 팔라듐 촉매를 사용하여 환상형 올레핀 단량체인 노보넨 (NB)과 5-비닐-2-노보넨(VNB)을 조성별로 비닐 부가 공중합하였다. 공중합체는 고수율과 고분자량 (M$_{w}$ > 760000)으로 얻을 수 있었다. VNB 함량이 많아질수록 공중합체의 분자량과 수득율은 감소하였으며, 첨가한 공단량체의 양과 공중합한 후 함유된 단량체의 양이 비례함을 FT-IR 분광분석으로 확인하였다. $^1$H-NMR 분석 결과 VNB는 exo, endo 이성체 모두 중합에 참여하는 것을 알 수 있었다. NB-VNB 공중합체의 분해 개시 온도는 약 300 $^{\circ}C$이었고, 열안정성은 VNB 함량과 관계없이 유사한 거동을 나타내었다. 합성된 NB-VNB 공중합체의 곁사슬 비닐기는 m-CPBA를 이용하여 에폭시화 하였고, 또한 9-BBN을 이용하여 수산화기를 도입하였다. 조성별 공중합체에 각각의 치환기가 도입된 것은 FT-IR, $^1$H-NMR 분석으로 확인하였다..

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

  • Park, Byeoung-Soo;Lee, Sung-Eun
    • 한국환경농학회지
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    • 제29권2호
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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.

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

  • 이민정;김대근;백형근;이강노;정규혁
    • Biomolecules & Therapeutics
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    • 제9권3호
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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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    • 제21권2호
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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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형태학적으로 고정된 뉴클레오사이드 주요중간체의 Enantioselective 합성법 탐색 (An Approach to the Enantioselective Synthesis of the Crucial Intermediate of Conformationally Locked Nucleosides)

  • 김순애;김학성
    • 약학회지
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    • 제54권6호
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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.

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

  • Lee, Jae-Rock;Jin, Fan-Long;Park, Soo-Jin
    • 한국복합재료학회:학술대회논문집
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    • 한국복합재료학회 2003년도 춘계학술발표대회 논문집
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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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    • 제30권10호
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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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    • 제15권2호
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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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    • 제32권1호
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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.