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Super-acidic Perfluorinated Resinsulfonic Acid (Nafion-H) Catalysis in Organic Synthesis

Research Project

Project/Area Number 10640526
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionSAGA UNIVERSITY

Principal Investigator

YAMATO Takehiko  Saga University, Faculty of Science and Engineering, Professor, 理工学部, 教授 (60136562)

Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2000: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1999: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsSolid superacid / Catalytic applications / Perfluororesinsulfonic acid / Nafion-H / Electrophilic reactions / Condensation / Rearrangements / Functionalized Nafion derivatives / ルイス酸触媒 / Friedel-Crafts反応 / Friedel-Drafts反応
Research Abstract

The catalytic applications of Nafion-H, a superacidic perfluororesinsulfonic acid in organic synthesis are investigated. Nafion-H, the acid form of a commercial Nafion-K ionomer, is a highly acidic (Ho ≧-12) solid catalyst superior to conventional resinsulfonic acids such as sulfonated polystylenes in its catalytic activity, thermal stability and chemical resistance.
Nafion-H catalyst is effective in a wide range of liquid and gas phase reactions, including electrophilic substitutions on aromatic nuclei, dehydration of alcohols, rearrangements, and polymerizations and so on. Nafion-H and related perfluoroalkanesulfonic acids are not only much stronger acids but sre also stable in corrosive enviroments and at temperature up to 210℃. Furthermore specific advantage of using insoluble resins as catalysts have been provided i) ease of by-product separation from the main reaction product usually by simple filtration ; ii) prevention of intermolecular reaction of reactive species or functional … More groups by simulating high dilution conditions ; iii) the possibility of reusing recovered reagents as well as eliminating the use of volatile or noxious substances. The presently developed procedure provides an excellent yield, easy isolation of the products, and ready regeneration of the catalyst without any loss of activity. Furthermore, the workup of the reaction mixture is extremely simple, involving filtration of the solid catalyst (which can be reused after simple regeneration). Only a catalytic amount of catalyst was needed instead of the usual stoichiometric quantity required for the conventional Lewis acid catalysts that bind to the hydroxyl droup or NH group. Specific advantages of using insoluble resins as catalysts include the prevention of intermolecular reactions of reactive species or functional groups by simulating high dilution conditions.
1. Super-acidic perfluorinated resinsulfonic acid (Nafion-H) catalysis in organic synthesis Nafion-H has been shown to be useful and versatile acid catalyst for organic reactions. It is effective in a wide range of liquid and gas phase reactions, including dehydration of alcohols, rearrangements, electrophilic substitutions on aromatic nuclei, and polymerizations. Especially, the presently developed procedure provides a range of application for the synthesis of macrocycles by Nafion-h catalyzed cyclibenzylation.
2. Development of functionalized Nafion derivatives We have developed an efficient and convenient procedure for oxidation of polycondensed aromatic hydrocarbons to quinones with Ce (IV) or Cr (III) impregnated Nafion-K catalyst using various co-oxidants, which are enable to proceed quite readily, giving good to moderate yields. The use of functionalized Nafion derivatives can be achieved various type of organic transformation. Less

Report

(4 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (47 results)

All Other

All Publications (47 results)

  • [Publications] Takehiko Yamato: "Synthesis, Conformational Studies and Inclusion Properties of O-Benzylated Calixarene-Analogous Trihydroxy [3.3.3] metacyclophanes"J.Chem.Soc.Perkin Trans.1. 609-614 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-Sized Cyclophanes.46.A Novel Thermal Rearrangement of Cyclophanes Having a Spiro Skeleton"J.Chem.Soc.Perkin Trans.1. 123-130 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Convenient Preparation of 14-Hydro-5H-tribenzo [a,d,f] cyclooctenes"Org.Prep.Proced.Int.. 30. 337-343 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Stable endoperoxide of 4,5,6,8,16-pentamethyl [2.2] metacyclophane ; structural analysis and deoxygenation"J.Chem.Soc.Perkin Trans.1. 1369-1371 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Synthesis and Ion Selectivity of Homocalixarenes"Journal Inclusion Phenomena. 32. 195-207 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Recent Developments of Perfluorinated Resinsulfonic Acid (Nafion-H) Catalysis in Organic Synthesis"Recent Research Development in Pure & Appl.Chem.. 2. 297-310 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "ipso-Nitration of tert-butyl [n.2] metacyclophanes ; through-space electronic interactions between two benzene rings"Canadian Journal of Chemistry. 76. 997-1005 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "ipso-Nitration of Hexahydroxy [(2.1)_3] metacyclophane, A Calixarene Analogous Macrocyclic Metacyclophane"Org.Prep.Proced.Int.. 31. 162-172 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-Size Cyclophanes, 49 Synthesis and Structures of [2.n] Metacyclophan-1,2-diones"New Journal of Chemistry. 24. 221-228 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.part 51.Acylation of [2.2] metaparacyclophanes : through-space electronic interactions between two benzene rings"Canadian Journal of Chemistry. 78. 238-247 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-Sized Cyclophanes.Part 53.Synthesis and Conformational Studies, and Photoinduced Cyclization of syn-[2.n] Metacyclophan-1-enes"Canadian Journal of Chemistry. 78. 1089-1099 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes, 55: Synthesis and conformational studies of [2.1.1] orthocyclophanes"New Journal of Chemistry. 25. 434-439 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Highly Efficient Nafion-Cerium (IV) or Nafion-Cr (III)-Catalyzed Oxidation of Polycondensed Aromatic Hydrocarbons with Co-oxidant"Journal of Chemical Research (S). 522-523 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.Part 56:5-tert-Butyl-8-substituted [2.2] metaparacyclophane-1,9-dienes,Preparation, X-ray diffraction studies, and their treatment with Lewis and protic acid"New Journal of Chemistry. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.Part 57.Synthesis, conformarions and stereodynamics of [2.n] Metacyclophan-1-enes and their conversion to [2.n] Metacyclophan-1-ynes"New Journal of Chemistry. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.Part 49.Synthesis and Conformational Studies of [2.n] Metacyclophan-1-enes and [n.1] Metacyclophanes"J.Chem.Soc.Perkin Trans.1. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, Y.Saruwatari, M.Yasumatsu and S.Ide: "Synthesis and Conformational Studies of Regio-and Conformational Isomers Derived from O-Benzylation of Tetrahydroxy [3.1.3.1] metacyclophanes"Eur.J.Org.Chem.. 309-316 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, M.Haraguchi, J.Nishikawa and S.Ide: "Synthesis, Conformational Studies and Inclusion Properties of O-Benzylated Calixarene-Analogous Trihydroxy [3.3.3] metacyclophanes"J.Chem.Soc.Perkin Trans.. 1. 609-614 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, N.Sakaue and Koji Fujita: "Convenient Preparation of 14-Hydro-5H-tribenzo [a, d, f] cyclo octenes"Org.Prep.Proced.Int.. 30. 337-343 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Sawada, K.Mimura, T.Thiemann, T.Yamato, M.Tashiro and S.Mataka: "Stable endoperoxide of 4,5,6,8,16-pentamethyl [2.2] metacyclophane ; structural analysis and deoxygenation"J.Chem.Soc.Perkin Trans.. 1. 1369 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato: "Synthesis and Ion Selectivity of Homocalixarenes"J.Inclusion Phenom.. 32. 195-207 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato: "Recent Developments of Perfluorinated Resinsulfonic Acid (Nafion-H) Catalysis in Organic Synthesis"Recent Research Development in Pure & Appl.Chem.. 2. 297-310 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, H.Kamimura, F.Zhang, and H.Tsuzuki: "ipso-Nitration of tert-butyl [n .2] metacyclophanes ; through-space electronic interactions between two benzene rings"Canadian Journal of Chemistry. 76. 997-1005 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, Y.Kinosaki and M.Yasumatsu: "ipso-Nitration of Hexahydroxy [(2.1)3] metacyclophane, A Calixarene Analogous Macrocyclic Metacyclophane"Org.Prep.Proced.Int.. 31. 162-172 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, K.Fujita, K.Okuyama and H.Tsuzuki: "Medium-Size Cyclophanes, 49 Synthesis and Structures of [2.n] Metacyclophan-1,2-diones"New Journal of Chemistry. 24. 221-228 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, K.Tokuhisa and H.Tsuzuki: "Medium-sized cyclophanes. part 51. Acylation of [2.2] metaparacyclophanes : through-space electronic interactions between two benzene rings"Canadian Journal of Chemistry. 78. 238-247 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, K.Fujita, K.Futatsuki and H.Tsuzuki: "Medium-Sized Cyclophanes. Part 53. Synthesis and Conformational Studies, and Photoinduced Cyclization of syn- [2.n] Metacyclophan-1-enes"Canadian Journal of Chemistry. 78. 1089-1099 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, N.Shinoda and T.Kanakogi: "Highly Efficient Nafion-Cerium (IV) or Nafion-Cr (III) -Catalyzed Oxidation of Polycondensed Aromatic Hydrocarbons with Cooxidant"J.Chem.Research (S). 522-523 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, N.Sakaue, K.Tanaka and H.Tsuzuki: "Medium-sized cyclophanes, 55 : Synthesis and conformational studies of [2.1.1] orthocyclophanes"New Journal of Chemistry. 25. 434-439 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, K.Noda, and H.Tsuzuki: "Medium-sized cyclophanes. Part 56 : 5-tert-Butyl-8-substituted [2.2] metaparacyclophane-1,9-dienes. Preparation, X-ray diffraction studies, and their treatment with Lewis and protic acid"New Journal of Chemistry. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato, K.Fujita, T.Abe and H.Tsuzuki: "Medium-sized cyclophanes. Part 57. Synthesis, conformarions and stereodynamics of [2.n] Metacyclophan-1-enes and their conversion to [2.n] Metacyclophan-1-ynes"New Journal of Chemistry. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Yamato and Koji Fujita: "Medium-sized cyclophanes. Part 49. Synthesis and Conformational Studies of [2.n] Metacyclophan-1-enes and [n.1] Metacyclophanes"J.Chem.Soc.Perkin Trans.. 1(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takehiko Yamato: "Medium-Size Cyclophanes,49 Synthesis and Structures of [2.n] Metacyclophan-1,2-diones"New Journal of Chemistry. 221-228 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.part 51.Acylation of [2.2] metaparacyclophanes : through-space electronic interactions between two benzene rings"Canadian Journal of Chemistry. 78. 238-247 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Takehiko Yamato: "Highly Efficient Nafion-Cerium(IV) or Nafion-Cr(III)-Catalyzed Oxidation of Polycondensed Aromatic Hydrocarbons with Co-oxidant"Journal of Chemical Research(S). 552-553 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.Part 54.Bromination of 5-tert-Butyl-8-methoxy[2.2] metaparacyclophane-1,9-diene and Dehydrobromination of the Bromine Adduct"Journal of Chemical Research. (S)14-15-(M)148-160 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes,55 : Synthesis and conformational studies of [2.1.1]orthocyclophanes"New Journal of Chemistry. (印刷中).

    • Related Report
      2000 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.Part 56 : 5-tert-Butyl-8-substituted[2.2]metaparacyclophane-1,9-dienes.Preparation,X-ray diffraction studies,and their treatment with Lewis acid and protic acid"New Journal of Chemistry. (印刷中).

    • Related Report
      2000 Annual Research Report
  • [Publications] Takehiko Yamato: "ipso-Nitration of Hexahydroxy[(2.1)_3]metacyclophane,A Calixarene Analogous Macrocyclic Metacyclophane"Org.Prep.Proced.Int.. 31. 162-172 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-Sized Cyclophanes.Part 49.Ο-Alkylation of 8,16-Dihydroxy-[2.2]metacyclophane"J.Chem.Research(S). 724-725 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-Sized cyclophanes.part 51.Acylation of [2.2]metaparacyclophanes: through-space electronic interactions between two benzene rings"Can.J.Chem.. 78. 238-247 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-Size Cyclophanes,49 Synthesis and Structures of [2.n]Metacyclophan-1,2-diones"New.J.Chem.. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] Takehiko Yamato: "Recent developments of perfluorinated resinsulfonic acid (Nafion-H) catalysis in organic synthesis" Recent Research Development in Pure & Appl.Chem.2. 297-310 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takehiko Yamato: "Convenient preparation of 14-hydro-5H-tribenzo[a,d,f]cyclooctenes" Org.Prep.Proced.Int.30. 337-343 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takehiko Yamato: "ipso-Nitration of tert-buty[n.2]metacyclophanes; through-space electronic interactions between two benzene rings" Can.J.Chem.76. 997-1005 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takehiko Yamato: "Medium-sized cyclophanes.46.A novel thermal rearrangement of cyclophanes having a spiro skeleton" J.Chem.Soc.Perkin Trans.1. 123-130 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takehiko Yamato: "ipso-Nitration of hexamrthoxy[(2.1)_3]metacyclophane,a calixarene analogous macrocyclic metacyclophane" Org.Prep.Proced.Int.(印刷中). (1999)

    • Related Report
      1998 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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