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1999 Fiscal Year Final Research Report Summary

SYNTHESIS OF NOVEL FLUORINATED COMPOUNDS BY THE USE OF ACTIVE FLUORINATING REAGENTS

Research Project

Project/Area Number 09305058
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionOKAYAMA UNIVERSITY

Principal Investigator

UNEYAMA Kenji  OKAYAMA UNIVERSITY, FACULTY OF ENGINEERING, PROFESSOR, 工学部, 教授 (00033150)

Co-Investigator(Kenkyū-buntansha) AMII Hideki  OKAYAMA UNIVERSITY, FACULTY OF ENGINEERING, ASSISTANT, 工学部, 助手 (00284084)
KATAGIRI Toshimasa  OKAYAMA UNIVERSITY, FACULTY OF ENGINEERING, ASSOCIATE PROFESSOR, 工学部, 助教授 (70202009)
Project Period (FY) 1997 – 1999
Keywordsfluorinated amino acid / defluorination / difluoromethylene / magnesium / フッ素化合物 / 有機電解
Research Abstract

1) C-F bond activation for the creation of difluoromethylene units Selective defluorination from trifluoromethyl group attached to p-system leading to the formation of difluoromethylene and defluorotrimethylsilylmethyl compounds has been developed. In particular, difluoroenolsilyl ethers, difluoroenamines, and 4'-trfluoromethy1, 1-difluorobenzy1 trimethylsilane nave been effectively prepared. The reductive reaction proceeded very smoothy1 by the action of two mole equivalents of metallic magnesium and four mole equivalents of TMS-C1 at 0℃ for 30 min. The industrially feasible production of difluorovinyl monomer for difluorovinyron and octafluoro [2.2 paracyclophane for flurorinated perarylene polymer would be realized.
2) Synthesis of optically active fluorinated amino acids Asymmetric reduction of imino group of 3, 3, 3-trifluoro-2-iminopropanoates was achieved by palladium catalyzed reduction in 3, 3, 3-trifluoroethanol which played an essentially important role for the asymmetric hydrogenation.
Syntheses of perfluoroalkylated α-diimines, 2, 2, 3, 3,-tetrafluoro-1, 4-diketones and pinacols.
Novel trifluoro- and perfluoroalkyl-α-diimines have been efficiently prepared by the palladium catalyzed coupling reaction of the corresponding imidoyl halides. The diimines could be a promising catalyst for polymerization of alkenes which would be studied in future. Likewise, difluoroenolsilyl ethers and trifluoromethyl ketones have been coupled by Cu (II) oxidation and Zn reduction, respectively.

  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] K. Uneyema, G. Mizutani: "Defluorinative silylation toward a selective preparation of α-Trimethyl-sylyl-α,α-difluoroacetates from trifluoroacetates"J. Chem. Soc., Chem. Commun.. 613-614 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H. Amii, T. Kobayashi, Y. Hatamoto, K. Uneyema: "Mg(O)-promoted selective C-F bond cleavage of trifluoromethyl ketones"J. Chem. Soc., Chem. Commun.. 1323-1324 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Katagiri, K. Kutose, N. Shimokawa, N. Kusumoto, K. Uneyema: "A Preparation of Trifluorolactic aldekyde"Tetrahedron. 55. 9163-9170 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Uneyema, G. Mizutani, K. Maeda, T. Kato: "Electroreductive Defluorination of Trifluoromethyl Ketones and Trifluoroacetic Acid Derivatives"J. Org. Chem.,. 64. 6717-6723 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Katagiri, M. Irie, K. Uneyema: "Intramolecular SN2 Reaction α-to a trifluoromethyl group Preparation of 1-Cyano-2-trifluoromethylcyclopropane"Tetrahedron : Asymmetry. 10. 2583-2589 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Katagiri, M. Takahashi, Y. Fujiwara, H. Ihara, K. Uneyema: "General Syntheses of Optically active α-Trifluoromethylated Amines via Ring Opening Reactions of N-Benzyl-2-trifluoromethylaziridine"J. Org. Chem.,. 64. 7323-7329 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Uneyema著,V.A. Soloshonok編: "Enantis controlled Synthesis of Fluoro-Organic Compounds"John Wiley & Sons. 673 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Uneyema著,S. Oae, A. Ohao, T. Okuyama編: "Reviews on Heteroatom Chemistry"Myu. 312 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Uneyama, G. Mizukami: "Defluorinative Silylation toward a Selective Preparation of α-Trimethylsilyl-α, α-difluoroacetates from Trifluoroacetates"Chem. Commun.. 613-614 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Amii, T. Kobayashi, Y. Hatamoto, K. Uneyama: "Mg (0)-promoted Selective C-F Bond Cleavage of Trifluoromethyl Ketones : a Conventional Method for the Synthesis of 2.2-Difluoro Enol Silanes"Chem. Commun.. 1323-1324 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Katagiri, K. Kutose, N. Shimokawa, N. Kusumoto: "A Preparation of Trifluorolactic Aldehyde"Tetrahedron. 55. 9163-9170 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Katagiri, M. Irie, K. Uneyama: "Intermolecular SィイD2NィエD22 Reaction α-to a Trifluoromethyl Group : Preparation of 1-Cyano-trifluoromethylcyclopropane"Tetrahedron Asymmetry. 10. 2583-2589 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Uneyama, G. Mizutani, K. Maeda, T. Kato: "Electroreductive Defluorination of Trifluoromethyl Ketones and Trifluoroacetic Acid Derivatives"J. Org. Chem.. 64. 6717-6723 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Katagiri, M. Takahashi, Y. Fujiwara, H. Ihara, K. Uneyama: "General Syntheses of Optically Activeα-Trifluoromethylated Amines via Ring-opening Reactions of N-Benzyl-2-trifluoromethylaziridine"J. Org. Chem.. 64. 7323-7329 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kenji Uneyama: "Chemistries of Trifluoroacetimidoyl Halides :Preparation, Reactions, and Applications for the Synthesis of Fluorinated Heterocycles"J. Fluorine Chem.. 97. 11-25 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Uneyama: "An Electrochemical Approach to the Synthesis of Fluorinated Organic Compounds"Reviews on Heteroatom Chemistry. 20. 1-26 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Uneyama and S. Hiraoka: "Reactions of Benzeneselenenyl Fluoride Generated by XeFィイD22ィエD2-(PhSe)ィイD22ィエD2 System with Electron-deficient Alkenes"J. Fluorine Chem.. (in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2001-10-23  

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