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Development of Novel Synthetic Methods of (Polyfluoro) silanes and Their Application to Creation of Functional Materials

Research Project

Project/Area Number 09450331
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionOsaka University

Principal Investigator

KOMATSU Mitsuo  Osaka Univ., Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (60029197)

Co-Investigator(Kenkyū-buntansha) RYU Ilhyong  Osaka Univ., Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (80210821)
KUNAI Atsutaka  Hiroshima Univ., Faculty of Engineering, Professor, 工学部, 教授 (90029190)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥14,000,000 (Direct Cost: ¥14,000,000)
Fiscal Year 1998: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 1997: ¥11,100,000 (Direct Cost: ¥11,100,000)
Keywordshalosilanes / fluorine-containing silanes / generation of 1,3-dipoles / heterocyclic compounds / silicon-containing polymers / functional materials / electron-transporting materials / heat-resistant materials / 含フッ素シラン / 1, 3-双様子発生 / シリレン / エーテル開環反応 / シクロ付加 / (ポリハロ)シラン / ブロモシラン / 有機ケイ素ポリマー / 耐熱性ポリマー / 1,3-双極子 / 複素環合成
Research Abstract

In this project are investigated development of new methods for synthesis of (polyfluoro)silanes, which bear more than two different functional groups, and their application to creation of functional materials such as heterocycles and organic silicon polymers. Major results obtained are summarized below.
1) Selective and efficient synthesis of a variety of hydrobromosilanes with high yields were achieved by treatment of hydrosilanes with copper bromide(II)/ copper iodide(I). Selective bromination of (polyhydro)silanes and (polyhydro)-
disilanes were also successful.
2) Highly efficient novel methodology for generation of azomethine ylides, typical 1,3-dipolar intermediates, utilizing di- or trifluorosilanes was found. Thus azaallyl anions or alpha-silylimines were treated with the fluorosilanes at room temperature to give azomethine ylides, which readily cycloadded to dipolaro-philes to afford various heterocycles.
3) Treatment of alpha-silylimidates, or in-situ generated imidates from alpha-silylamides, with trifluorosilanes caused generation of azomethine ylide intermediates even at room temperature and their cycloadditions afforded a variety of heterocycles.
4) To develop silicon-containing polymeric materials, synthetic methods of poly(silylenephenylene)s bearing Si-Cl and Si-F bonds were established. Various functional groups were introduced onto silicon atoms by nucleophilic displacement of the halogen moieties. Among them, a polymer containing ethynylphenyl functionality showed excellent heat-resistant ability.
5) Several silicon-bridged bithiophenes were unprecedently synthesized via difluorosilane derivatives and this class of compounds are good candidates for electron-transportaing materials.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report

Research Products

(23 results)

All Other

All Publications (23 results)

  • [Publications] M.Komatsu: "Hydroxymethylation of Organic Halides. Evaluation of a Catalytic System Involving a Fluorous Tin Hydride Reagent for Radical Carbonylation" Tetrahedron Lett.38・45. 7883-7886 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Komatsu: "Silica Gel-PromotedSynthesis of 1, 4-Oxathiane Derivatives from β, β′-Dichloro Sulfides" Heterocycles. 47・1. 133-137 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Komatsu: "Yb (OTf) _3-Catalyzed 1, 3-Dipolar Cycloaddition of Nitrone with Alkene ; Switch in Diastereoselectivity by Solvent and Bidentate Auxiliary" Tetrahedron Lett.39・29. 5205-5208 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Komatsu: "Iodine-Catalyzed Aziridinarion of Alkenes using Chloramine-T as a Nitrogen Source" Tetrahedron. 54・44. 13485-13494 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Komatsu: "Novel Asymmetric and Stereospecific Aziridination of Alkenes with a Chiral Nitridomanganese Complex" Angew.Chem.Int.Ed.Engl.37・24. 3392-3394 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Kunai: "Preparation and Reactions of Poly [(ethoxysilylene) phenylenes] and Thermal Properties of the Resulting Polymers." Macromolecules. 30・6. 1540-1549 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Kunai: "Synthesis and Properties of Dithienosiloles." J.Organomet.Chem.553. 487-491 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Kunai: "Synthesis and Optical, Electrochemical, and Electron-Transportiig Properties of Silicon-Bridged Bithiophenes." Organometallics. 18 印刷中. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mitsuo Komatsu: "Hydroxymethylation of Organic Halides. Evaluation of a Catalytic System Involving a Fluorous Tin Hydride Reagent for Radical Carbonylation" Tetrahedron Lett.38(45). 7883-7886 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mitsuo Komatsu: "Silica Gel-Promoted Synthesis of 1,4-Oxathiane Derivatives from beta, beta'-Dichloro Sulfides" Heterocycles. 47(1). 133-137 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mitsuo Komatsu: "Yb(OTf)_3-Catalyzed 1,3-Dipolar Cycloaddition of Nitrone with Alkene ; Switch in Diastereoselectivity by Solvent and Bidentate Auxiliary" Tetrahedron Lett.39(29). 5205-5208 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mitsuo Komatsu: "Iodine-Catalyzed Aziridinarion of Alkenes using Chloramine-T as a Nitrogen Source" Tetrahedron. 54(44). 13485-13494 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mitsuo Komatsu: "Novel Asymmetric and Stereospecific Aziridination of Alkenes with a Chiral Nitridomanganese Complex" Angew.Chem.Int.Ed.Engl.37(24). 3392-3394 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Preparation and Reactions of Poly [(ethoxysilylene) phenylenes] and Thermal Properties of the Resulting Polymers." Macromolecules. 30(6). 1540-1549 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Synthesis and Properties of Dithienosiloles." J.Organomet.Chem.553. 487-491 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Atsutaka Kunai: "Synthesis and Optical, Electrochemical, and Electron-Transporting Properties of Silicon-Bridged Bithiophenes." Organometallics. 18(in press). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M. Komatsu: "Nitrogen Atom Transfer to Alkenes Utilizing Chloramine-T as Nitrogen Source" Tetrahedron Lett.39・3/4. 309-312 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M. Komatsu: "Yb (OTT) _3-Catalyzed 1, 3-Dipolar Cycloaddition of Nitrone with Alkene ; Switch in Diastercoselectivity by Solvent and Bibcntate Auxiliary" Tetrahedron Lett.39・29. 5205-5208 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M. Komatsu: "Iodine-Catalyzed Aziridinarion of Alkenes using Chloramine-T as a Nitrogen Source" Tetrahedron. 54・44. 13485-13494 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M. Komatsu: "Novel Asymmetric and Stereospecific Aziridination of Alkenes with a Chiral Nitridomanganese Complex" Angew. Chem. Int. Ed. Engl.37・24. 3392-3394 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] A. Kunai: "Synthesis and Properties of Dithienosiloles" J. Organomet. Chem.553. 487-491 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] A. Kunai: "Synthesis and Optical, Electrochemical, and Electron-Transporting Properties of Silicon-Bridged Bithiophenes" Organometallics. 18 (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] J.Ohshita: "Preparation and Reactions of Poly[(ethoxysilylene)phenylenes] and Thermal Properties of the Resulting Polymers." Macromolecules. 30・6. 1540-1549 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-03-31   Modified: 2016-04-21  

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