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Synthesis of Supramolecular Compounds and Novel Siloxanes Starting from Silanols

Research Project

Project/Area Number 12640510
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionDepartment of Applied Chemistry, Faculty of Engineering, Gunma University

Principal Investigator

UNNO Masafumi (2001-2002)  Gunma University ; Applied Chemistry, Associate Professor, 工学部, 助教授 (20251126)

海野 雅史 (2000)  群馬大学, 工学部, 助手 (25201126)

Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2002: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2001: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2000: ¥800,000 (Direct Cost: ¥800,000)
Keywordsladdersiloxanes / stereospecific synthesis / cyclic silanols / supramolecular aggregates / nano tube and wire / thermal stability / functional material / selective synthesis / シロキサン / シラノール / 超分子 / 水素結合 / ラダーシロキサ / 固体反応
Research Abstract

1. Synthesis of novel silanols.
Following novel silanols were prepared, isolated, and their structures were determined ; Silanetriols, RSi(OH)_3, Disiloxanetetraols, (RSi(OH)_2O)_2 (R=i-Pr, Mes, Tip, cyclohexyl) ; Cyclotetrasiloxanetetraol, (i-PrSi(OH)O)_4 (all four isomers) ; Incompletely condensed silsesquioxanes, T_3(OH)_3, T_4(OH)_2, and T_5(OH).
2. Supramolecular aggregates composed of silanols.
Co-crystallization or recrystallization from mixed solvent gave novel hydrogen-bonded supramolecular aggregates : all-cis-(i-PrSi(OH))_4 and i-Pr_2Si(OH)_2, cis,trans-(TipSi(OH)O)_3 from MeOH/THF, cis,trans,cis-(i- PrSi(OH)O)_4, cis, trans, cis-(i-PrSi(OH)O)_4.
3. Synthesis of polycyclic laddersiloxanes.
By applying our new method (stepwise construction of laddersiloxanes), the first functionalized tricyclic laddersiloxanes and pentacyclic laddersiloxane were synthesized. The structures of the Tetraphenyl and tetrahydroxyl tricyclic laddersiloxanes, and pentacyclic laddersiloxane were determined by X-ray crystallography. In addition, reaction with separated diastereomer made it possible to construct first heptcyclic and nonacyclic laddersiloxanes.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] M.Unno, A.Suto, H.Matsumoto: "Pentacyclic Laddersiloxane"J.Am.Chem.Soc.. 124. 1574-1575 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] R.Tanaka, S.Kyushin, M.Unno, H.Matsumoto: "Chiral Crystallization of anti-Dodecaisopropyltricyclo-[4.2.0.0^<2,5>]octasilane"Enantiomer. 7. 157-159 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Yamada, M.Unno, K.Kobayashi, H.Oku, H.Yamamura, S.Arai, H.Matsumoto, R.Katakai, M.Kawai: "Stereochemistry of Protected Ornithine Side Chains of Gramicidin S Derivatives : X-ray Crystal Structure of the Bis-Boc-tetra-N-methyl Derivatives of Gramicidin"J.Am.Chem.Soc.. 124. 12684-12688 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Unno, T.Saito, H.Matsumoto: "Synthesis and Crystal Structures of Silapericyclynes"Bull.Chem.Soc.Jpn.. 74. 2407-2413 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Unno, Y.Kawai, H.Matsumoto: "Synthesis and Crystal Structures of 2,4,6-Tri-tert-butylphenyltrichlorogermane and 2,4,6-Tri-tert-butylphenylgermane"Heteroatom Chem.. 12. 238-243 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Unno, K.Negishi, H.Matsumoto: "Extended Silapericyclynes"Chem.Lett.. 340-341 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Akiko Suto, and Hideyuki Matsumoto: "Penta-cyclic Laddersiloxane"J. Am. Chem. Soc.. 124. 1574-1575 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Ryoji Tanaka, Soichiro Kyushin, Masafumi Unno, and Hideyuki Matsumoto: "Chiral crystallization of anti-dodecaisopropyltricyclo[4.2.0.0^<2.5>]octasi Iane"Enantiomer. 7. 157-159 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Keiichi Yamada, Masafumi Unno, Kyoko Kobayashi, Hiroyuki Oku, Hatsuo Yamamura, Shuki Araki, Hideyuki Matsumoto, Ryoichi Katakai, and Masao Kawai: "Stereochemistry of Protected Omithine Side Chains of Gramicidin S Derivatives : X-ray Crystal Structure of the Bis-Boc-tetra-N-methyl Derivatives of Gramicidin S"J. Am. Chem. Soc.. 124. 12684-12688 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Yuuki Kawai, and Hideyuki Matsumoto: "Synthesis and Crystal Structures of 2,4,6-Tri-tert-butylphenyltrichlorogermane and 2,4,6-Tri-tert-butylphenylgermane"Heteroatom Chem.. 12. 238-243 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Takashi Saito, and Hideyuki Matsumoto: "Synthesis and Crystal Structures of Silapericyclynes"Bull Chem. Soc. Jpn.. 74. 2407-2413 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Keisuke Negishi, and Hideyuki Matsumoto: "Extended Silapericyclynes"Chem. Lett.. 340-341 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Koichi Higuchi, Koji Furuya, Hiroaki Shioyama, Soichiro Kyushin, Midori Goto, and Hideyuki Matsumoto: "Synthesis, Structure, and Reactions of Octakis(1,1,2-trimethylpropyl)octagermacubane"Bull. Chem. Soc. Jpn.. 73. 2093-2097 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Soichiro Kyushin, Akira Meguro, Masafumi Unno, and Hideyuki Matsumoto: "Photolysis of anti-Dodecaalkyltricyclo[4.2.0.0^<2.5>]octasilane : Generation and Reactions of Cyclotetrasilene"Chem. Lett.. 494-495 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Hiroaki Horiuchi, Yukio Nakano, Takayoshi Matsumoto, Masafumi Unno, Hideyuki Matsumoto, and Hiroshi Hiratsuka: "Electronic Structure and Photochemical Reaction Intermedises of Octakis(1,1,2-trimethylpropyl)octasilacubane"Chem. Phys, Lett.. 322. 33-40 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Keisuke Takada, and Hideyuki Matsumoto: "Formation of Supramolecule by Assembling of Two Different Silanols"Chem. Lett.. 242-243 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Masafumi Unno, Akiko Suto, Keisuke Takada, and Hideyuki Matsumoto: "Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetrahydroxycyclotetrasiloxane"Bull. Chem. Soc. Jpn.. 73. 215-220 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Unno, A.Suto, H.Matsumoto: "Pentacyclic Laddersiloxane"J. Am. Chem. Soc. 124. 1574-1575 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Tanaka, S.Kyushin, M.Unno, H.Matsumoto: "Chiral Crystallization of anti-Dodecaisopropyltricyclo-[4.2.0.0^<2,5>]octasilane"Enantiomer. 7. 157-159 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Yamada, M.Unno, K.Kobayashi, H.Oku, H.Yamamura, S.Arai, H.Matsumoto, R.Katakai, M.Kawai: "Stereochemistry of Protected Ornithine Side Chains of Gramicidin S Derivatives : X-ray Crystal Structure of the Bis-Boc-tetra-N-methyl Derivatives of Gramicidin"J. Am. Chem. Soc.. 124. 12684-12688 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Masafumi Unno, Akiko Suto, Hideyuki Matsumoto: "Pentacyclic Laddersiloxane"J. Am. Chem. Soc.. (in press). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masafumi Unno, Takashi Saito, Hideyuki Matsumoto: "Synthesis and Crystal Structures of Silapericyclynes"Bull. Chem. Soc. Jpn.. (in press). (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masafumi Unno, Yuuki Kawai, Hideyuki Matsumoto: "Synthesis and Crystal Structures of 2,4,6-Tri-tert-butylphenyltrichlorogermane and 2,4,6-Tri-tert-butylphenylgermane"Heteroatom Chem.. 12. 238-243 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Masafumi Unno, Keisuke Negishi, Hideyuki Matsumoto: "Extended Silapericyclynes"Chem. Lett.. 340-341 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hiroaki Horiuchi, Yukio Nakano, Takayoshi Matsumoto, Masafumi Unno, Hideyuki Matsumoto, Hiroshi Hiratsuka: "Electronic Structure and Photochemical Reaction Intermediates of Octakis(1,1,2-trimethylpropyl)octasilacubane"Chem. Phys. Lett.. 322. 33-40 (2000)

    • Related Report
      2001 Annual Research Report
  • [Publications] 久新, 海野, 松本 (分担): "「有機ケイ素素材料科学の新展開」第10章 ラダー構造を有するポリシラン及びポリシロキサン"シーエムシー. (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Unno,A.Suto,K.Takada,and H.Matsumoto: "Synthesis of Ladder and Cage Silsesquioxanes from 1. 2. 3. 4-Tetraydroxycycloterasiloxane"Bull.Chem.Soc.Jpn.. 73. 215-220 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Unno,K.Takada,and H.Matsumoto: "Formation of Supermolecule by Assembling of Two Different Silanols"Chem.Lett.. 242-243 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Unno,K.Higuchi,K.Furuya,H.Shioyama,S.Kyushin,M.Goto,and H.Matsumoto: "Synthesis, Structure, and Reactions of Octakis (1, 1, 2-trimethylpropyl) octagermacubane,"Bull.Chem.Soc.Jpn.. 73. 2093-2097 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Kyushin,A.Meguro,M.Unno,and H.Matsumoto: "Photolysis of anti-Dodecaalkyltricyclo [ 4.2.0.0^<2.15>] octasilane : Generation and Reactions of Cyclotetrasilene"Chem.Lett.. 494-495 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Matsumoto,S.Kyushin,M.Unno,and R.Tanaka: "Syntheses, Structures, and Properties of Ladder Oligosilanes and Ladder Oligogermanes"J.Organomet.Chem.. 611. 52-63 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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