• Title/Summary/Keyword: epoxidation

Search Result 102, Processing Time 0.029 seconds

Synthesis of Periodic Mesoporous Organosilica by Microwave Heating

  • Yoon, Sang-Soon;Son, Won-Jin;Biswas, Kalidas;Ahn, Wha-Seung
    • Bulletin of the Korean Chemical Society
    • /
    • v.29 no.3
    • /
    • pp.609-614
    • /
    • 2008
  • A periodic mesoporous organosilica material was synthesized by microwave heating (PMO-M) using 1,2-bis(trimethoxysilyl)ethane as a precursor in a cationic surfactant solution, and textural properties were compared with those of the product produced by conventional convection heating (PMO-C). These synthesized materials were characterized using XRD, TEM/SEM, N2 adsorption isotherm, 29Si and 13C NMR, and TGA, which confirmed their good structural orders and clear arrangements of uniform 3D-channels. Synthesis time was reduced from 21 h in PMO-C to 2-4 h in PMO-M. PMO-M was made of spherical particles of 1.5-2.2 m m size, whereas PMO-C was made of decaoctahedron-shaped particles of ca. 8.0 m m size. Effect of synthesis temperature, time, and heating mode on the PMO particle morphology was examined. The particle size of PMO-M could be controlled by changing the heating rate by adjusting microwave power level. PMO-M demonstrated improved separation of selected organic compounds compared to PMO-C in a reversed phase HPLC experiment. Ti-grafted PMO-M also resulted in higher conversion in liquid phase cyclohexene epoxidation than by Ti-PMO-C.

Selective Epoxidation and Reduction of Rigid Cyclic ${\alpha},{\beta}$-Unsaturated Carbonyl Compounds (환상 ${\alpha},{\beta}$-불포화 카르보닐 화합물의 선택적 에폭시화 및 환원)

  • Ma, Eun-Sook
    • YAKHAK HOEJI
    • /
    • v.49 no.6
    • /
    • pp.443-448
    • /
    • 2005
  • Diosgenin (25 (R) - spirost-5-en-3$\beta$ -ol) was oxidized with 2,3-dichloro -5,6-dicyano-1,4-benzoquinone to form 25(R)-1,4,6-spirostatrien-3-one (1) as rigid cyclic $\alpha$,$\beta$-unsaturated carbonyl compound. This compound was reacted with $H_{2}O_{2}$, m-chloroperoxybenzoic acid (mCPBA), NaOCl in the presence with (R,R)- or (S,S)-Jacobsen catalyst, tert-butyl-hydroperoxide (TBHP) in Mo$(CO)_{6}$, and in VO $(acac)_{2}$ catalyst, respectively, 25(R) -1,4,6-spirostatrien -3-one (1) was reduced with $NaBH_{4}$ L-Selectride, $LiAIH_{4}$,$BH_{3}$ $\cdot$$(CH_{3})_{2}S$, Superhydride, Red-Al, and lithium tri-tert-butoxyaluminium hydride. And 25(R)-4,6-spirostadien-3$\beta$-ol (4) was treated with $H_{2}O_{2}$, mCPBA, TBHP in D - (-) - and L-(+)-diisopropyltar-trate and $Ti(OiPr)_{4}$ condition (Sharpless asymmetric epoxidation), TBHP in $Mo(CO)_{6}$, and in $VO(acac)_{2}$ catalyst, respectively.

Metalloporphyrin Catalyzed Olefin Epoxidation and Molecular Orbital Study (Metalloporphyrin의 Olefin Epoxidation과 분자궤도함수론적 고찰)

  • Hwhan Jin Yeo;Hyun Chun Sin
    • Journal of the Korean Chemical Society
    • /
    • v.36 no.4
    • /
    • pp.558-564
    • /
    • 1992
  • Product yields were determined for the reaction of styrene with sodium hypochlorite (NaOCl) in CH$_2$Cl$_2$ with various substituted manganese porphyrin complexes as catalysts. In the presence of the electron withdrawing group and ortho-substituted manganese porphyrin complexes, reaction rate and epoxide selectivity are increased. Also reaction rate and epoxide selectivity are largely increased by the presence of imidazole which behaves as axial ligand of the manganese porphyrin complexes. By the kinetic study with Michealis-Menten equation, the factor significantly affected to catalytic ability is $K_m$ value. A large binding affinity consists with the low $K_m$. With theoretical analysis by EHMO calculation, the results are in good agreement with experimental data.

  • PDF

Syntheses of Oxirane Carboxylic Acids as Hypoglycemic agents

  • 서영거;백소영;민경훈;신동윤;정재경
    • Proceedings of the Korean Society of Applied Pharmacology
    • /
    • 1997.04a
    • /
    • pp.75-75
    • /
    • 1997
  • 뛰어난 혈당강하작용을 가지고 있는 oxirane carboxilic acid의 analogue 합성과 관련하여 oxirane carboxilic acid의 기본골격을 용이하게 형성할 수 있고 동시에 다앙한 관능기를 갖는 side chain을 도입할 수 있는 방법을 개발함으로써 다양한 유도체들을 합성하는데 이용하고자 함. 방법 및 결과 $\alpha$,$\beta$-unsaturated ester로부터 dioxirane을 이용한 직접적인 epoxidation을 통해서 보통의 방법으로는 얻기 어려운 oxirane carboxilic acid의 ester를 높은 수율로 합성할 수 있는 방법이 개발되었으며 특히 분자내에 cpoxide 존재하에서도 Mitsnobu 방법을 이용한 O-alkylation에 의해 aryl ether 결합을 형성할 수 있는 방법이 개발되었으며 이들 방법을 이용하여 다양한 유도체들을 합성하였다.

  • PDF

Synthesis of 11-Deoxydaunomycinone and Novel 10-Fluoroanthracyclinone Derivatives

  • Rho, Young S.;최영희;김규일;신홍식;유동진;정채준;김선하
    • Bulletin of the Korean Chemical Society
    • /
    • v.20 no.5
    • /
    • pp.551-555
    • /
    • 1999
  • 11-Deoxydaunomycinone 15 and 10-fluoroanthracyclinone derivatives 9, 10 were obtained. Naphthalenone 4 prepared from 2-(2,4-pentadienyl)-1,3-dioxane 2 with methyl vinyl ketone and hydrolysis with HClO4 was condensed with phthalidesulfone 5 through Michael type reaction, and was converted to 7 by epoxidation. Epoxide 7 was transformed to trione 12 using reduction-oxidation or hydrofluorination process, and then to 15 by introducing several functional groups. Compound 8 obtained in the course of the reaction of epoxide 7 and HF/ Pyr was used for the synthesis of compounds 9, 10.

Chiral Synthesis of Costunolide

  • Sumaila Abu;Jeong, Jin-Hyun;Shin, Dong-Hyok
    • Proceedings of the PSK Conference
    • /
    • 2002.10a
    • /
    • pp.363.1-363.1
    • /
    • 2002
  • Costunolide. a sesquiterpene lactone is isolated from Magnolia Sieboldi. It is known to possess antitumour and anti-inflammatory activities. This compound is synthesized from Ihe easily available decalin dione using the ring cleavage approach to construct the ten-membered ring system. The two keys points in this work are the chiral inductionon the allyl alcohol moiety using Sharpless epoxidation reaction and opening of the eopxide with an organocuprate reagent which leads to a $\alpha$-exomethylene lactone. (omitted)

  • PDF

Reagentselective and positionselective epoxidation of 25(R)-1,4,6-spirostatrien-3-one and 25(R)-4,6-spirostadien-3$\beta$-ol

  • Ma, Eun-Sook;Kim, Hak-Soon;Kim, Eun-Jung;Jung, Won-Young
    • Proceedings of the PSK Conference
    • /
    • 2003.04a
    • /
    • pp.233.2-233.2
    • /
    • 2003
  • Diosgenin(25(R)-spirost-5-en-3${\beta}$-ol) is the steroid saponin, was isolated from Mexican yam(Oioscorea). Estrogenic, progesterogenic and anti-inflammatory effects of diosgenin has been hypothesized due to its structural similarity to estrogen, progesterone precursors. And diosgenin had been reported to lower serum cholesterol in chicken and rabbits fed cholesterol and to decrease liver cholesterol in cholesterol-fed rats. (omitted)

  • PDF

A Deep Investigation of the Thermal Decomposition Process of Supported Silver Catalysts

  • Jiang, Jun;Xu, Tianhao;Li, Yaping;Lei, Xiaodong;Zhang, Hui;Evans, D.G.;Sun, Xiaoming;Duan, Xue
    • Bulletin of the Korean Chemical Society
    • /
    • v.35 no.6
    • /
    • pp.1832-1836
    • /
    • 2014
  • A deep understanding of the metallic silver catalysts formation process on oxide support and the formation mechanism is of great scientific and practical meaning for exploring better catalyst preparing procedures. Herein the thermal decomposition process of supported silver catalyst with silver oxalate as the silver precursor in the presence of ethylenediamine and ethanolamine is carefully investigated by employing a variety of characterization techniques including thermal analysis, in situ diffuse reflectance infrared Fourier transform spectroscopy, scanning electron microscopy, and X-ray diffraction. The formation mechanism of supported silver particles was revealed. Results showed that formation of metallic silver begins at about $100^{\circ}C$ and activation process is essentially complete below $145^{\circ}C$. Formation of silver was accompanied by decomposition of oxalate group and removal of organic amines. Catalytic performance tests using the epoxidation of ethylene as a probe reaction showed that rapid activation (for 5 minutes) at a relatively low temperature ($170^{\circ}C$) afforded materials with optimum catalytic performance, since higher activation temperatures and/or longer activation times resulted in sintering of the silver particles.