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Heterogeneously catalyzed selective synthesis of aromatic amines and aromatic azides from aryl halides using the same azide as the nitrogen source

Research Project

Project/Area Number 24590015
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionGifu Pharmaceutical University

Principal Investigator

MONGUCHI Yasunari  岐阜薬科大学, 薬学部, 准教授 (40433205)

Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2014: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2013: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2012: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Keywords芳香族第一級アミン / 芳香族アジド / 不均一系触媒 / 銅 / 機能性物質 / 触媒・化学プロセス / 有機化学 / 合成化学
Outline of Final Research Achievements

The selective synthetic methods for the preparation of aromatic azides and aromatic amines based on the kinds of heterogeneous copper catalysts were established. Copper catalysts supported on chelate resins bearing iminodiacetate moieties (DIAION CR11) or polyamine moieties (DIAION CR20) as chelating functional groups (12% Cu/CR11 and 7% Cu/CR20, respectively) were developed. 12% Cu/CR11 effectively catalyzed the cross-coupling reaction between various iodoarenes and sodium azide to generate the corresponding aryl azides in good yields, although it was very difficult to achieve by precedent methods using homogeneous copper catalysts due to the unexpected amine formations. On the other hand, use of 7% Cu/CR20 as the catalyst led to the selective formation of aromatic primary amines by the reductive amination of iodoarenes with sodium azide without any additives.

Report

(4 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • 2012 Research-status Report
  • Research Products

    (5 results)

All 2013 2012 Other

All Journal Article (1 results) (of which Peer Reviewed: 1 results) Presentation (2 results) (of which Invited: 1 results) Remarks (2 results)

  • [Journal Article] Solvent-free Huisgen cyclization using heterogeneous copper catalysts supported on chelate resins2013

    • Author(s)
      Yasunari Monguchi
    • Journal Title

      Green Chemistry

      Volume: 15 Issue: 2 Pages: 490-495

    • DOI

      10.1039/c2gc36584g

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Presentation] Heterogeneous Transition Metal Catalysts Supported on Organic Polymers: Hydrogenation, Cross-Coupling, and Cycloaddition2013

    • Author(s)
      Yasunari Monguchi
    • Organizer
      International Congress for Innovation in Chemistry (PERCH-CIC Congress VIII)
    • Place of Presentation
      Pattaya, Thailand
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] 芳香族第一級アミン及び芳香族アジドの選択的合成法2012

    • Author(s)
      門口泰也
    • Organizer
      第101回有機合成シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2012 Research-status Report
  • [Remarks] 岐阜薬科大学 創薬化学大講座 薬品化学研究室

    • URL

      http://www.gifu-pu.ac.jp/lab/yakuhin/index.html

    • Related Report
      2014 Annual Research Report
  • [Remarks] 岐阜薬科大学 創薬化学大講座 薬品化学研究室

    • URL

      http://www.gifu-pu.ac.jp/lab/yakuhin/

    • Related Report
      2012 Research-status Report

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Published: 2013-05-31   Modified: 2019-07-29  

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