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2006 Fiscal Year Final Research Report Summary

No-Solvent Synthesis of Siloxanes and Silicone Nanotube

Research Project

Project/Area Number 15350020
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionGunma University

Principal Investigator

UNNO Masafumi  GUNMA UNIVERSITY, Faculty of Engineering, PROFESSOR, 工学部, 教授 (20251126)

Project Period (FY) 2003 – 2006
Keywordssiloxane / no-solvent reaction / green chemistry / silanol / regulation of structure / functional material / silsesquioxane / supramolecular structure
Research Abstract

In this project, we aimed the syntheses of highly regulated silanols, and transformation to the novel siloxanes like nano-tube siloxanes by means of no-solvent reaction.
Through this research, we obtained the following new result and published them.
1)The stereospecific new reaction we invented made possible the synthesis of six-membered silanol, cyclotrisiloxanetriols (all two isomers) and eight-membered silanol, cyclotetrasiloxanetetraols (all four isomers). These are all new compounds, and especially cyclotetrasiloxanetetraols are very good precursors of ladder silsesquioxanes. Starting cyclotetrasiloxanetetraols, we obtained pentacyclic, heptacyclic, nonacyclic, and polycyclic laddersiloxanes. These are next-generation thermostable materials with low dielectric constant. We are currently investigation the application.
2)By investigating starting compounds and reagents, we could extend the no-solvent reaction to the common synthesis of siloxanes. For example, the reaction of silanols with p-toluenesulfonic acid afforded strained siloxanes those could not be obtained by usual solution reaction. Additionally, hydrobromic acid and hydroiodic acid are good additives for the preparation of siloxanes inaccessible by solvent reactions. With these results, we can utilize cost-saving environmental-friendly no-solvent reaction of siloxanes.

  • Research Products

    (27 results)

All 2007 2006 2005 2004 2003

All Journal Article (26 results) Book (1 results)

  • [Journal Article] Synthesis of Laddersiloxanes by Novel Stereocontrolled Approach2007

    • Author(s)
      M.Unno, T.Matsumoto, H.Matsumoto
    • Journal Title

      Journal of Organometallic Chemistry 692

      Pages: 307-312

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of cyclic bis- and Trismelamine Derivatives and Their Complexation properties with Barbiturates2007

    • Author(s)
      S.Kondo, T.Hayashi, Y.Sakuno, Y.Takezawa, T.Yokoyama, M.Unno, Y.Yano
    • Journal Title

      Organic and Biomolecular Chemistry 5

      Pages: 907-916

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Novel Pd-Catalyzed Atom-Efficient Cross-Coupling Reaction by Means of Hexaarylcyclotrisiloxane2007

    • Author(s)
      M.Endo, T.Sakurai, S.Ojima, T.Katayama, M.Unno, H.Matsumoto, S.Kowase, H.Sano, M.Kosugi, K.Fugami
    • Journal Title

      Synlett 5

      Pages: 749-752

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis of Laddersiloxanes by Novel Stereocontrolled Approach2007

    • Author(s)
      M.Unno, T.Matsumoto, H.Matsumoto
    • Journal Title

      Org.Biomol.Chem. 5

      Pages: 907-916

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Novel Pd-Catalyzed Atom-Efficient Cross-Coupling Reaction by Means of Hexaarylcyclotrisiloxane2007

    • Author(s)
      M.Endo, T.Sakurai, S.Ojima, T.Katayama, M.Unno, H.Matsumoto, S.Kowase, H.Sano, M.Kosugi, K.Fugami
    • Journal Title

      SynLett 5

      Pages: 749-752

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of cyclic bis- and Trismelamine Derivatives and Their Complexation properties with Barbiturates2007

    • Author(s)
      S.Kondo, T.Hayashi, Y.Sakuno, Y.Takezawa, T.Yokoyama, M.Unno, Y.Yano
    • Journal Title

      Org.Biomol.Chem. 5

      Pages: 907-916

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Anion Recognition by a Silanediol-Based Receptor2006

    • Author(s)
      S.Kondo, T.Harada, R.Tanaka, M.Unno
    • Journal Title

      Organic Letters 8

      Pages: 4621-4624

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Anion Recognition by a Silanediol-Based Receptor2006

    • Author(s)
      S.Kondo, T.Harada, R.Tanaka, M.Unno
    • Journal Title

      Org.Lett. 8

      Pages: 4621-4624

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Borderline of Hydrogen Bonding by Silanols2005

    • Author(s)
      M.Unno, H.Murakami, S.Kagawa, H.Matsumoto
    • Journal Title

      Silicon Chemistry 3

      Pages: 195-198

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and Structures of the First Titanium(IV) Complexes with Cyclic Tetrasiloxide Ligands : Incomplete and Complete Cage Titanosiloxanes2005

    • Author(s)
      M.Hirotsu, S.Taruno, T.Yoshimura, K.Ueno, M.Unno, H.Matsumoto
    • Journal Title

      Chem. Lett. 34

      Pages: 1542-1543

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Stereoisomers of 1,3,5,7-Tetrahydroxy-1,3,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal2005

    • Author(s)
      M.Unno, Y.Kawaguchi, Y.Kishimoto, H.Matsumoto
    • Journal Title

      J. Am. Chem. Soc. 127

      Pages: 2256-2263

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Oligocyclic Laddersiloxanes : Alternative Synthesis by Oxidation2005

    • Author(s)
      M.Unno, R.Tanaka, S.Tanaka, T.Takeuchi, S.Kyushin, H.Matsumoto
    • Journal Title

      Organometallics 24

      Pages: 765-768

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] cis-trans-cis-Tetrabromotetramethylcyclotetra- siloxane : a Versatile Precursor of Ladder Silsesquioxanes2005

    • Author(s)
      M.Unno, S.Chang, H.Matsumoto
    • Journal Title

      Bull. Chem. Soc. Jpn. 78

      Pages: 1105-1109

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Supramolecular aggregates of silanols and solid-state synthesis of siloxanes2005

    • Author(s)
      M.Unno, K.Takada, Y.Kawa-guchi, H.Matsumoto
    • Journal Title

      Molecular Crystals and Liquid Crystals 440

      Pages: 259-264

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Synthesis and Structures of the First Titanium(IV) Complexes with Cyclic Tetrasiloxide Ligands : Incomplete and Complete Cage Titanosiloxanes2005

    • Author(s)
      M.Hirotsu, S.Taruno, T.Yoshimura, K.Ueno, M.Unno, H.Matsumoto
    • Journal Title

      Chem.Lett. 34

      Pages: 1542-1543

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Borderline of Hydrogen Bonding by Silanols2005

    • Author(s)
      M.Unno, H.Murakami, S.Kagawa, H.Matsumoto
    • Journal Title

      Silicon Chem. 3

      Pages: 195-198

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] cis-trans-cis-Tetrabromotetramethylcyclotetra- siloxane : a Versatile Precursor of Ladder Silsesquioxanes2005

    • Author(s)
      M.Unno, S.Chang, H.Matsumoto
    • Journal Title

      Bull.Chem.Soc.Jpn. 78

      Pages: 1105-1109

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Stereoisomers of 1,3,5,7-Tetrahydroxy-1,3,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal2005

    • Author(s)
      M.Unno, Y.Kawaguchi, Y.Kishimoto, H.Matsumoto
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 2256-2263

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Triisopropylcyclotrisiloxanetriol : An Unprecedented Cyclic Siloxanetriol with Relatively Small Substituents2004

    • Author(s)
      M.Unno, Y.Kishimoto, H.Matsumoto
    • Journal Title

      Organometallics 23

      Pages: 6221-6224

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Hexakis(2,4,6-triisopropylphenylsilsesquioxane)2004

    • Author(s)
      M.Unno, Y.Imai, H.Matsumoto
    • Journal Title

      Silicon Chem. 2

      Pages: 175-178

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Photo-initiated Bromination of octakis(1,1,2-trimethylpropyl)octasila-cubane with Tetrabromomethane2004

    • Author(s)
      M.Unno, H.Masuda, H.Matsumoto
    • Journal Title

      Silicon Chem. 1

      Pages: 377-381

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] The Cyclo[(disilanylene)(butadiyne)]s [(i-Pr)_2Si(i-Pr)_2SiC≡CC≡C]_n (n=2-4)2004

    • Author(s)
      K.Negishi, M.Unno, H.Matsumoto
    • Journal Title

      Chem. Lett. 33

      Pages: 430-431

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Triisopropylcyclotrisiloxanetriol : An Unprecedented Cyclic Siloxanetriol with Relatively Small Substituents2004

    • Author(s)
      M.Unno, Y.Kishimoto, H.Matsumoto
    • Journal Title

      Organometallics 12723

      Pages: 6221-6224

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] The Cyclo[(disilanylene)(butadiyne)]s [(i-Pr)_2Si(i-Pr)_2SiC≡CC≡C]_n(n=2-4)2004

    • Author(s)
      K.Negishi, M.Unno, H.Matsumoto
    • Journal Title

      Chem.Lett. 33

      Pages: 430-431

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Tip-substituted Cage and Cyclic Silanols2003

    • Author(s)
      M.Unno, T.Tanaka, H.Matsumoto
    • Journal Title

      J.Organomet.Chem. 686

      Pages: 175-182

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Structure and Oxidation of Octakis(tert-butyldimethylsilyl)octasilacubane2003

    • Author(s)
      M.Unno, T.Matsumoto, K.Mochizuki, K.Higuchi, M.Goto, H.Matsumoto
    • Journal Title

      J.Organomet.Chem. 685

      Pages: 156-161

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] 新時代への視点 -群馬大学研究室から-2006

    • Author(s)
      群馬大学地域連携推進室編
    • Total Pages
      312
    • Publisher
      上毛新聞社
    • Description
      「研究成果報告書概要(和文)」より

URL: 

Published: 2008-05-27  

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