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Developmental Research on Scale-up in Electrochemical Fluorination

Research Project

Project/Area Number 02555179
Research Category

Grant-in-Aid for Developmental Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionOkayama University

Principal Investigator

UNEYAMA Kenji  Okayama University, Faculty of Engineering, Department of Applied Chemistry Professor, 工学部, 教授 (00033150)

Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥9,400,000 (Direct Cost: ¥9,400,000)
Fiscal Year 1991: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1990: ¥8,800,000 (Direct Cost: ¥8,800,000)
KeywordsFluorination / Electrooxidation / Trifluoromethylation / フッ素化 / フッ素化合物 / 電気化学 / 有機電解合成 / トリフルオロ
Research Abstract

Developmental Research on Scale-up in Electrochemical Fluorination
This research consists of mainly two programs. The first is development of new electrochemical perfluoromethylation of olefins in a small sacle reactions and the second is a scale-up electrolysis of electrochemical trifluoromethylation, of methyl acrylate in 0. I kg scale by a flow cell electrolysis system.
Electrochemical perfluoroalkylations of methyl acrylate, acrylamide, and acrylonitrile have been investigated. Perfluorooctanoic, butanoic, and difluoroacetic acids provided dimers of the corresponding perfluorinated carbon radicals in reasonable yields. In the oxygen atmosphere the electrolysis gave 2-oxo or. 2-hydroxy-4, 4, 4-trifluorobutylates in 30 - 45 % yields. This oxy-trifluoromethylation is promising for preparation of some valuable trifluoromethyl compounds otherwise difficult to prepare.
A flow cell equipped with 10 X 10 cm^2 platinated titanium plates as electrodes was employed for 0. I Kg scale electrolysis of TFA and methylacrylate to give 50 % of the desired products at the current densities of 50 - 80 mA/cm^2. The temperature of the electrolysis affects current efficiency intensively. The lower temperature at around 0 C is desirable for the purpose.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] Kenji Uneyama: "Electrochemical Trifluoromethylation of Olefins;Product-selectivity and Mechanistic Aspects" Tetrahedron. 45. 555-562 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Po-Chung Cheng,Tsutomu Nonaka, Kenju Uneyama: "Trifluoromethylation of Olefins in a Flow cell" DENKI KAGAKU. 59. 427-430 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama,Masafumi Kobayashi: "Synthesis of 1-Aryl-2-trifluoromethylbenzimidazoles via Electrochemically Prepared p-Benzoquinone Imines" Tetrahedron Letters. 32. 5981-5982 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama,Shunsuke Watanabe,Kouichi Kitagawa,Yukio Tokunaga,Yasuhiro Sato: "Perfluoroalkylation of Olefins by electrooxidation of Perfluoroalkanoic Acids;Relation between Product-selectivity and Current Density and Structure of Olefins" Bull.Chem.Soc.Jpn.,.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama,Masafumi Kobayashi: "Electrochemical Oxidation of N,N-Disubstituted Trifluoroacetamidic Acid;An Approach to N-Substituted 2-trifluoromethyl Benzimidaloes" J.Am.Chem.Soc.,.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama: "Recent Development of Trifluoromethylation" J.Synth.Org.Chem.Jpa.,. 49. 612-623 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama: "Electrochemical Trifluoromethylation of Olefins ; Product-selectivity and Mechanistic Aspects" Tetrahedron. 45(4/5). 555-562 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Po-Chung Cheng, Tsutomu Nonaka, and Kenji Uneyama: "Trifluoromethylation of Olefins in a Flow cell" Denkikagaku. 59(5). 427-430 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama and Masafumi Kabayashi: "Synthesis of 1-Aryl-2-trifluoromethylbenzimidazoles via Electrochemically Prepared p-Benzoquinone Imines." Tetrahedron Letters. 32(42). 5981-5982 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama, Shunsuke Watanabe, Kouichi Kitagawa, Yukio Tokunaga, and Yasuhiro Sato: "Perfluoroalkylation of Olefins by Electrooxidation of Perfluoroalkanoic Acids ; Relation between Product-selectivity and Current Density and Structure of Olefins." Bull. Chem. Soc. Jpn.(1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama and Masafumi Kobayashi: "Electrochemical Oxidation of N, N-Disubstituted Trifluoroacetamidic Acids ; An Apporoach to N-Substituted 2-trifluoromethyl Benzimidaloes." J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kenji Uneyama: "Recent Development of Trifluoromethylation" J. Synth. Org. Chem. Jpn.49. 612-623 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 宇根山 健治: "ELECTROCHEMICAL TRIFLUOROMETHYLATION OF OLEFINS;PRODUCT-SELECTIVITY AND MECHANISTIC ASPECTS" Tetrahedron. 47. 555-562 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 宇根山 健治: "Syntheses of 1-Aryl-2-trifluoromethylbenzimidazoles via Electrochemically Prepared P-Benzoquinone Imines" Tetrahedron Letters. 32. 5981-5982 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 宇根山 健治: "Perfluoroalkylation of Olefins by Electrooxidation of Perfuoroalkane Carboxylic Acidsi Relations between Product-selectivity and Current Density and Structures of Olefins" Bull.Chem.Soc.Jpn.

    • Related Report
      1991 Annual Research Report
  • [Publications] 宇根山 健治: "トリフルオロメチル化反応の最近の進展" 有機合成化学協会誌. 49. 612-623 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Uneyama,S.Watanabe,Y.Tokunaga,K.Kitagawa: "Perfluoroalkylation of Olefins by Electrochemical Oxidation of Perfluoroalkane Carboxylic acids." Journal of the Organic Chemistry.

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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