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Environmentally Friendly Electroorganic Synthesis in Ionic Liquids Toward a Solvent-Free Process

Research Project

Project/Area Number 16550090
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

FUCHIGAMI Toshio  Tokyo Institute of Technology, Department of Electronic Chemistry, Professor, 大学院・総合理工学研究科, 教授 (10016701)

Co-Investigator(Kenkyū-buntansha) TAJIMA Toshiki  Tokyo Institute of Technology, Department of Electronic Chemistry, Assistant Professor, 大学院・総合理工学研究科, 助手 (50361770)
Project Period (FY) 2004 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2005: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2004: ¥1,900,000 (Direct Cost: ¥1,900,000)
KeywordsIonic liquid / Fluoride salt / Anodic fluorination / Photocatalytic degradation / Co salen mediator / Electrocatalytic debromination / Fluorodesulfurization / Ultrasonication / 有機電解合成 / イオン液体 / 電極触媒 / コバルト錯体 / メディエーター / ニトロキシルラジカル / 脱ハロゲン化 / グリーンケミストリー / 溶媒効果 / 含フッ素カーボナート / 含フッ素エーテル / 電解反応 / フッ化糖
Research Abstract

Solvent free electroorganic synthesis is highly desirable from an environmental aspect. In recent years, room-temperature molten salts, namely ionic liquids, have proved to be a new class of promising solvents because of their good electroconductivity, nonflammability, thermal stability, nonvolatality, and reusability. Therefore, when ionic liquids are used as electrolytic media, organic electrolytic reactions, particularly electroorganic synthesis should be possible without any organic solvents. However, there have been still a limited number of papers dealing with organic electrosynthesis in ionic liquids. In this project, we have achieved the following subjects.
1) Anodic fluorodesulfurization of 3-phenylthiophthalide, 4-phenylthio-1,3-dioxolan-2-one, and 1-arylthio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside in ionic liquids like Et_3N・nHF (n=4,5) and Et_4NF・nHF (n=4,5) without any solvents provided the corresponding monofluorinated products exclusively in moderate to good yields. In … More sharp contrast, the anodic fluorination in Et_3N・3HF with and without co-solvent resulted in α-fluorination without desulfurization exclusively or preferentially. It was also demonstrated that the electrochemical fluorodesulfurization of 3-phenylthiophthalide under solvent free conditions was achieved repeatedly four times by the reuse of a fluoride salt, Et_4NF・4HF. Thus, we have shown the first example of fluorodesulfurization by the reuse of an ionic liquid fluoride salt. (n=4,5).
2) The catalytic effect of a Co(II)salen mediator on the reduction of cyclic vio-dibromide was investigated in ionic liquids by cyclic volteammetry. Macro-scale controlled potential electrolysis gave the corresponding debrominated product in moderate to good yields. The workup after electrolysis in an ionic liquid proved to be much simpler than that in organic solvents. The possibility of reruse of the ionic liquid was demonstrated to some extent.
3) Photocatalytic degradation of organic pollutants such as naphthol blue black, Amarance, and 2-chlorophenol (2CP) was carried out using TiO_2 in ionic liquids. The phtocatalytic degradation rate of the former two azo dyes were greatly enhanced in ionic liquids compared with those in water. In sharp contrast, the photodegradation of 2CP was not efficient in an ionic liquid, however, the degradation was enhanced under simultaneous ultrasonication.
4) Anodic fluorination of cyclic thiocarbonates like 1,3-oxathiolane-2one was successfully carried out in ionic liquids like Et_4NF・4HF. Less

Report

(3 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • Research Products

    (27 results)

All 2006 2005 2004

All Journal Article (22 results) Book (5 results)

  • [Journal Article] Anodic α-Fluorination of Five-Membered Cyclic Thiocarbonates2006

    • Author(s)
      Yi Cao
    • Journal Title

      Electrochimica Acta 51

      Pages: 2477-2482

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Electrochemical Partial Fluorination of Organic Compounds. Anodic α-Fluorination of Five-Membered Cyclic Thiocarbonates2006

    • Author(s)
      Y.Cao, T.Tajima, T.Fuchigami
    • Journal Title

      Electrochim.Acta 51

      Pages: 2477-2482

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Highly Selective Electrochemical Fluorination of Organic Compounds in Ionic LIquids2005

    • Author(s)
      Toshio Fuchigami
    • Journal Title

      Journal of Fluorine Chemistry 126・2

      Pages: 181-187

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Highly Regioselective Electrochemical Fluorination of Organic Compounds in Ionic Liquids2005

    • Author(s)
      T.Fuchigami, T.Tajima
    • Journal Title

      J.Fluorine Chem. 126

      Pages: 181-187

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Ionic Liquids-Mysterious Salts2005

    • Author(s)
      T.Kitazume, T.Fuchigami, H.Sawada, T.Ito
    • Journal Title

      Corona Publisher

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrolytic Reactions2005

    • Author(s)
      T.Fuchigami
    • Journal Title

      Electrochemical Aspects of Ionic Liquids (Ed.H.Ohno) (John Wiley & Sons)

      Pages: 89-109

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Highly Selective Electrochemical Fluorination of Organic Compounds in Ionic Liquids2005

    • Author(s)
      Toshio Fuchigami
    • Journal Title

      Journal of Fluorine Chemistry 126・2

      Pages: 181-187

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Anodic Fluorodesulfurization of Phthalide, Ethylene carbonate, and Glucopyranosides Having Arylthio Groups2004

    • Author(s)
      Masaru Hasegawa
    • Journal Title

      Electrochimica Acta 49

      Pages: 3367-3372

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrocatalytic DEbromination of Organic Bromides Using a Cobal(II) Salen Complex in Ionic LIquids2004

    • Author(s)
      Yi Shen
    • Journal Title

      Electrochemistry 72・12

      Pages: 849-851

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photocatalytic Degradation of Organic Pollutants in Room-Teperature Ionic Liquids2004

    • Author(s)
      Kei Sekiquchi
    • Journal Title

      Electrochmeistry 72・12

      Pages: 839-839

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] イオン性液体を反応メディアとする」有機電解合成2004

    • Author(s)
      淵上 寿雄
    • Journal Title

      化学工業 55・11

      Pages: 839-845

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] イオン性液体を用いた有機電解合成2004

    • Author(s)
      淵上 寿雄
    • Journal Title

      機能材料 24・11

      Pages: 20-26

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrolytic Reactions in Ionic Liquids. 5. Anodic Fluorodesulfurization of Phthalide, Ethylene Carbonate, and Glucopyranosides Having Arylthio Groups2004

    • Author(s)
      M.Hasegawa, T.Fuchigami
    • Journal Title

      Electrochim.Acta 49

      Pages: 3367-3372

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrocatalytic Debromination of Organic Bromides Using a Cobalt(II)salen Complex in Ionic Liquids2004

    • Author(s)
      Y.Shen, T.Tajima, M.Atobe, T.Fuchigami
    • Journal Title

      Electrochemistry 72

      Pages: 849-851

    • NAID

      10013631987

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photocatalytic Degradation of Organic Pollutants in Room-Temperature Ionic Liquids2004

    • Author(s)
      K.Sekiguchi, M.Atobe, T.Fuchigami
    • Journal Title

      Electrochemistry 72

      Pages: 839-842

    • NAID

      10013631942

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electroorganic Synthesis using Ionic Liquids as Reaction Media2004

    • Author(s)
      T.Fuchigami
    • Journal Title

      Chemical Industry 55

      Pages: 839-845

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electroorganic Synthesis Using Ionic Liquids2004

    • Author(s)
      T.Fuchigami
    • Journal Title

      Function & Materials 24, No.11

      Pages: 20-26

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electrolytic Reactions in Ionic Liquids2004

    • Author(s)
      T.Fuchigami, M.Atobe
    • Journal Title

      New Developments in organic Electrosysthesis (T.Fuchigami, Ed.) (CMC, Tokyo)

      Pages: 229-241

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] ELECTROORGANIC REACTION IN IONIC LIQUIDS, S.ANODIC FLUORO-DESULFURIZATION OF PHTHALIDE ETHYLENE CARBONATE, AND GLUCOPYRANOSIDES HAVING ARYLTHIO GBOUPS2004

    • Author(s)
      MASARU HASEGAWA
    • Journal Title

      ELECTROCHIMICA ACTA 49

      Pages: 3367-3372

    • Related Report
      2004 Annual Research Report
  • [Journal Article] ELECTROCATACYTIC DEBROMINATION OF ORGANIC BROMIDES USING A COBALT(II)SACEN COMPLEX IN IONIC LIQUIDS2004

    • Author(s)
      Y, SHEN
    • Journal Title

      ELECTROCHMISTRY 72・12

      Pages: 849-851

    • Related Report
      2004 Annual Research Report
  • [Journal Article] イオン性液体を反応メディアとする有機電解合成2004

    • Author(s)
      淵上寿雄
    • Journal Title

      化学工業 55・11

      Pages: 839-845

    • Related Report
      2004 Annual Research Report
  • [Journal Article] イオン性液体を用いた有機電解合成2004

    • Author(s)
      淵上寿雄
    • Journal Title

      機能材料 24・11

      Pages: 20-26

    • Related Report
      2004 Annual Research Report
  • [Book] Electrochemical Aspects of Inoic LIquids2005

    • Author(s)
      Hiroyuki Ohno
    • Total Pages
      294
    • Publisher
      John Weily & Sons
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] イオン液体-常識を覆す不思議な塩2005

    • Author(s)
      北爪 智哉
    • Total Pages
      154
    • Publisher
      コロナ社
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Book] Electrochemical Aspects of Ionic Liquids2005

    • Author(s)
      Toshio Fuchigami
    • Total Pages
      392
    • Publisher
      Wiley Interscience
    • Related Report
      2005 Annual Research Report
  • [Book] イオン液体-常識を覆す不思議な塩-2005

    • Author(s)
      北爪智哉
    • Total Pages
      154
    • Publisher
      コロナ社
    • Related Report
      2004 Annual Research Report
  • [Book] 有機電解合成の新展開2004

    • Author(s)
      淵上 寿雄
    • Total Pages
      295
    • Publisher
      シーエムーシー出版
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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