• Title/Summary/Keyword: Chemical cyclization

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Kinetic Study of Cyclization of High-Tacticity Polyacrylonitrile Heat-Treated under Air Atmosphere via XRD (공기분위기 하에서 열처리된 고입체 규칙성 폴리아크릴로니트릴의 XRD에 의한 환화반응 속도 연구)

  • Xu, Zhi-Xian;Xu, Jing;Xu, Liang-Hua;Dai, Yong-Qiang;Xue, Li-Wei;Jin, Ri-Guang
    • Polymer(Korea)
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    • v.32 no.2
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    • pp.150-156
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    • 2008
  • Two different polyacrylonitrile samples (PANs, triad tacticity fraction is 0.25 and 0.64) were synthesized and used to study the kinetics of cyclization. Polymers were treated at different temperatures between 250 to $300^{\circ}C$ under air atmosphere, and analyzed by X-ray diffractometer. The sharp and strong peak at $2{\theta}=16.5^{\circ}$ corresponds to a lateral repeat distance that is the (100) diffraction in hexagonal lattice, while the peak at $2{\theta}=25.5^{\circ}$ reflects the (101) diffraction. In comparing their areas of different heat treated samples, the cyclization of both PANs was identified as a first-order reaction. The rate constants of cyclization reaction at different temperatures and the active energy parameter were obtained. This results might provide an important effect on pre-oxidation of polyacrylonitrile fiber.

Mn(III)-Mediated Radical Cyclization for Δ1-3-Octalone Synthesis

  • Lee, Mi-Ai;Yang, Jae-Deuk;Kim, Moon-Soo;Jeon, Hye-Sun;Baik, Woon-Phil;Koo, Sang-Ho
    • Bulletin of the Korean Chemical Society
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    • v.23 no.5
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    • pp.736-740
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    • 2002
  • An efficient and practical synthetic method of △1 -3-octalone, which is a versatile building block for thesyntheses of polycyclic compounds, has been developed. The dianion of ethyl acetoacetate reacts with cyclohexene-1-carboxaldehyde (3) to produce the aldol adduct 6, which then undergoes Mn(Ⅲ)-mediated radical cyclization followed by acetate elimination to give △1 -3-octalone 4. A detailed mechanistic insight of Mn(Ⅲ)-mediated cyclization of 6 has been disclosed.

A Systematic Study on Knoevenagel Reaction and Nazarov Cyclization of Less Reactive Carbonyl Compounds Using Rare Earth Triflates and Its Applications

  • Ilangovan, A.;Muralidharan, S.;Maruthamuthu, S.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.1000-1006
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    • 2011
  • A systematic study of Knoevenagel reaction and Nazarov cyclization was made on variety of less reactive carbonyl compounds such as ${\beta}$-ketoesters, 1,3-diketones and cyclic active methylene compounds using $Yb(OTf)_3$ as the catalyst. Recycling study confirms reusability of the catalyst without much loss of activity.

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.

A Convenient Synthesis of New 3,7-Diphenylthieno[3,2-e]bis[1,2,4] triazolo[4,3-a:4',3'-c]pyrimidine Derivatives by Oxidative Cyclization Using Alumina-supported Calcium Hypochlorite

  • Son, Hoon-Young;Song, Yang-Heon
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2242-2246
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    • 2010
  • New 3,7-diphenylthieno[3,2-e]bis[1,2,4]triazolo[4,3-a:4',3'-c]pyrimidine derivatives were easily synthesized at room temperature in good yield by the oxidative cyclization of thienopyrimidinyl hydrazones with alumina-supported calcium hypochlorite ($Ca(OCl)_2/Al_2O_3$).