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Novel Synthetic Methodology Utilizing Fluorous Phases as a Liquid Screen

Research Project

Project/Area Number 15550095
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka Prefecture University

Principal Investigator

MATSUBARA Hiroshi  Osaka Prefecture University, Department of Chemistry, Associate Professor, 総合科学部, 講師 (20239073)

Co-Investigator(Kenkyū-buntansha) RYU Ilhyong  Osaka Prefecture University, Department of Chemistry, Professor, 総合科学部, 教授 (80210821)
Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 2004: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2003: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywordsperfluoroalkane / bromination / fluorous / Friedel-Crafts acylation / phase-vanishing method / Galden / demethylation / parallel synthesis / フェイズバニシング法 / ジアステレオ選択性 / 4塩化スズ
Research Abstract

In this project, we studied "the Phase-Vanishing(PV) Method". This novel method that we developed recently utilizes unique properties of the fluorous phase. The PV method, which capitalizes on the diffusion of reagents through the fluorous phase, is very simple methodology, and does not need any dropping funnels, heating/cooling baths, and thermometers. Inspection of suitable solvent for the PV method reveals that FC-72(perfluorohexanes) is an outstanding fluorous solvent. Firstly we examined bromination of olefins with Br2 ; this reaction finished in 2 days with standing to afford corresponding dibromide in 68-97% yields, while gentle stirring of the bromine layer, taking care not to mix the three layers, the reaction completed in 4 hours giving similar yields (88-91%). We also carried out various organic reactions including demethylations of aryl methyl ethers with BBr_3, bromination of alcohols with PBr_3 or SOBr_3, and the Friedel-Crafts acylations of aromatic compounds with SnCl_4 using the PV method, and showed that the method gave corresponding products in good yields. A parallel synthesis of the PV method in the Friedel-Crafts acylations using a very simple multi-fingered glass apparatus is also performed successfully, providing four types of aromatic keteones in high yield (64-85%) at once. During this project with FC-72 we have found that the solvent has weak points. Namely, the recovery of FC-72 is invaluably incomplete due to its high volatility, and in the parallel synthesis we sometimes faced contamination of products. In order to overcome these problems, we searched again more suitable fluorous solvents for the PV method than FC-72, and found that perfluoropolyethers (Galden) are a superior solvent.

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (15 results)

All 2005 2004 2003 Other

All Journal Article (12 results) Book (2 results) Publications (1 results)

  • [Journal Article] Theoretical Study on the Isomerization Behavior between α,β-Unsaturated Acyl Radicals and a-Ketenyl Radicals.2005

    • Author(s)
      H.Matsubara, I.Ryu, C.H.Schiesser
    • Journal Title

      J.Org.Chem. 70(9)

      Pages: 3610-3617

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Acetylene carbonylation by radicals : tin radical catalyzed synthesis of a-methylene amides from 1-alkynes, carbon monoxide, and amines2005

    • Author(s)
      Y.Uenoyama, T.Fukuyama, O.Nobuta, H.Matsubara, I.Ryu
    • Journal Title

      Angew.Chem.Int.Ed. 44(7)

      Pages: 1075-1078

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Theoretical Study on the Isomerization Behavior between α,β-Unsaturated Acyl Radicals and α-Ketenyl Radicals2005

    • Author(s)
      H.Matsubara, I.Ryu, C.H.Schiesser
    • Journal Title

      J.Org.Chem. 70(9)

      Pages: 3610-1617

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Mizoroki-Heck arylation of a,b-unsaturated acids with a hybrid fluorous ether, F-626 : Facile filtrative separation of products and efficient containing a catalyst recycling of a reaction medium2004

    • Author(s)
      T.Fukuyama, M.Arai, H.Matsubara, I.Ryu
    • Journal Title

      J.Org.Chem. 69(23)

      Pages: 8105-8107

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Mizoroki-Heck arylation of a,b-unsaturated acids with a hybrid fluorous ether, F-626 : Facile filtrative separation of products and efficient recycling of a reaction medium containing a catalyst2004

    • Author(s)
      T.Fukuyama, M.Arai, H.Matsubara, I.Ryu
    • Journal Title

      J.Org.Chem. 69(23)

      Pages: 8105-8107

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Mizoroki-Heck Arylation of a, b-Unsaturated Acids with a Hybrid Fluorous Ether, F-626 : Facile Filtrative Separation of Products and Efficient Recycling of a Reaction2004

    • Author(s)
      T.Fukuyama, M.Arai, H.Matsubara, I.Ryu
    • Journal Title

      Journal of the Organic Chemistry 69(23)

      Pages: 8105-8105

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Intramolecular Homolytic Translocation Chemistry : An ab Initio Study of 1,n-Silyl, Germyl, and Stannyl Group Transfer containing a catalyst2003

    • Author(s)
      H.Matsubara, C.H.Schiesser
    • Journal Title

      J.Org.Chem. 68(24)

      Pages: 9299-9309

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Fluorous solvent as a new phase-screen medium between reagents and reactants in the bromination and chlorination of alcohols2003

    • Author(s)
      H.Nakamura, T.Usui, H.Kuroda, I.Ryu, H.Matsubara, S.Yasuda, D.P.Curran
    • Journal Title

      Org.Lett. 5(8)

      Pages: 1167-1169

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Phase-Vanishing method : Friedel-Crafts acylation of thiophene with tin tetrachloride and its application to convenient parallel synthesis2003

    • Author(s)
      H.Matsubara, S.Yasuda, I.Ryu
    • Journal Title

      Synlett. (2)

      Pages: 247-249

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Intramolecular Homolytic Translocation Chemistry : An ab Initio Study of 1,n-Silyl, Germyl, and Stannyl Group Transfer and Related Ring-closure Reactions2003

    • Author(s)
      H.Matsubara, C.H.Schiesser
    • Journal Title

      J.Org.Chem. 68(24)

      Pages: 9299-9309

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Phase-vanishing method : Friedel-Crafts acylation of thiophene with tin tetrachloride and its application to convenient parallel synthesis2003

    • Author(s)
      H.Matsubara, S.Yasuda, I.Ryu
    • Journal Title

      Synlett (2)

      Pages: 247-249

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Two types of intramolecular homolytic substitution reactions at group XIV atoms : unusual radical 1,4-Sn shifts from Si to C and carbonylative SHi reaction at Si2003

    • Author(s)
      Studer, S.Amrein, H.Matsubara, C.H.Schiesser, T.Doi, T.Kawamura, T.Fukuyama, I.Ryu
    • Journal Title

      Chem.Commun.

      Pages: 1190-1191

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] Handbook of Fluorous Chemistry2004

    • Author(s)
      I.Ryu, H.Matsubara, D.P.Curran
    • Total Pages
      593
    • Publisher
      Wiley-VCH
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] Handbook of Fluorous Chemistry2004

    • Author(s)
      I.Ryu, H.Matsubara, D.P.Curran
    • Total Pages
      593
    • Publisher
      Wiely-VCH
    • Related Report
      2004 Annual Research Report
  • [Publications] H.Matsubara, S.Yasuda, I.Ryu: "Phase-Vanishing Method. Friedel-Crafts Acylation of Thiophene with Tin Tetrachopride and Its Application to Convenient Parallel Synthesis"Synlett. 247-249 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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