触媒膜導入マイクロ流路反応デバイスの創製

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 22106544
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Institute for Molecular Science
• Principal Investigator: 魚住 泰広 分子科学研究所, 生命・錯体分子科学研究領域, 教授 (90201954)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2011: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2010: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: マイクロ・リアクター / 固体化触媒 / 高速化触媒 / フロー・リアクター / 膜触媒

Research Abstract

平成23年度には、マイクロ流路内での膜状高分子錯体の調製(step1)、ナノパラジウム触媒膜の形成(step2)と、同膜触媒導入マイクロ流路デバイスを利用する反応実施(step3)の3段階について検討した。具体的にはstep1では高分子配位子として直鎖ポリビニルピリジンおよびテトラクロロパラデートをY字型マイクロ流路に導入しマイクロ流路層流界面上で良好な膜形成が進行した。流路内で調製した触媒膜を還元的あるいは熱的に分解することで高分子膜内でのパラジウムナノ粒子の発生を試みた(step2)。
その結果、PVP-Pd膜を50℃、30分間、ギ酸ナトリウム水溶液で扱うことで比較的狭いサイズ分布を持ったナノPd粒子が発生することを見いだした。さらに流路内に調製したナノPd膜を備えたマイクロ流路反応装置を利用し、幾つかのPd触媒工程をフロー型反応として試みた(step3)。
その結果、ハロアレーン類の還元的脱ハロ反応がギ酸を還元剤として有効に働くことを見いだした。すなわちハロアレーン水溶液とギ酸水溶液をマイクロデバイスY字同入口から各々加えたところ室温で反応は速やかに進行流路内の保持時間僅か2-5秒で定量的に脱ハロ生成物を与えた。芳香族ハライドの置換基として電子供与性、電子求引性、オルト位、メタ位、パラ位に関わらず反応は良好であり、また芳香環上に複数のクロロ基を有する基質も良い反応性を示した。さらに本反応はハロアレーン濃度が10ppm程度でも問題なく進行した。

Research Products

• [Journal Article] Self-Assembled Poly(imidazole-palladium) : Highly Active, Reusable Catalyst at Parts per Milion to Parts per Billion Levels (2012)
  • Author(s): Uozumi Y
  • Journal Title: J.Am.Chem.Soc. Volume: 134 Issue: 6 Pages: 3190-3198
  • DOI: 10.1021/ja210772v
  • Peer Reviewed
• [Journal Article] Tandem Olfin Migration-Aldol Condensation in Water with an Amphiphilic Resin-Supported Ruthenium Complex (2011)
  • Author(s): Uozumi, Y
  • Journal Title: Synlett Volume: 2011 Issue: 06 Pages: 787-790
  • DOI: 10.1055/s-0030-1259689
  • Peer Reviewed
• [Journal Article] Molecular-architecture-Based Administration of Catalysis in Water : Self-Assembly of an Amphiphilic Palladium Pincer Complex (2011)
  • Author(s): Uozumi, Y
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50 Issue: 21 Pages: 4876-4878
  • DOI: 10.1002/anie.201100827
  • Peer Reviewed
• [Journal Article] Recovery of in situ-generated Pd Nanoparticles with Linear Polystyrene (2011)
  • Author(s): Uozumi Y
  • Journal Title: Green and Sustainable Chemistry Volume: 1 Pages: 19-25
  • Peer Reviewed
• [Journal Article] C-N and C-S Bond Forming Cross Coupling in Water with Amphiphilic Resin-supported Palladium Complexes (2011)
  • Author(s): Uozumi Y
  • Journal Title: Chem.Lett. Volume: 40 Issue: 12 Pages: 934-935
  • DOI: 10.1055/s-0031-1289410
  • NAID: 10029521706
  • Peer Reviewed
• [Journal Article] Highly Active Copper-Network Catalyst for the Direct Aldol Reaction (2011)
  • Author(s): Uozumi Y
  • Journal Title: Chem.Asian J Volume: 6 Issue: 9 Pages: 2545-2549
  • DOI: 10.1002/asia.201100284
  • Peer Reviewed
• [Journal Article] A novel amphiphilic pincer palladium complex : design, preparation and self-assembling behavior (2011)
  • Author(s): Uozumi Y
  • Journal Title: Dalton Trans. Volume: 40 Issue: 35 Pages: 8859-8868
  • DOI: 10.1039/c1dt10556f
  • Peer Reviewed
• [Journal Article] In-Water Dehydrative Alkylation of Ammonia and Amines with Alcohols by a Polymeric Bimetallic Catalyst (2011)
  • Author(s): Uozumi Y
  • Journal Title: Org.Lett. Volume: 13 Issue: 15 Pages: 3892-3895
  • DOI: 10.1021/ol201422s
  • Peer Reviewed
• [Journal Article] A Highly Active and Reusable Self-Assembled Poly (Imidazole/Palladium) Catalyst : Allylic Arylation/Alkenylation (2011)
  • Author(s): Uozumi Y
  • Journal Title: Angew.Cham.Int.Ed. Volume: 50 Issue: 40 Pages: 9437-9441
  • DOI: 10.1002/anie.201103799
  • Peer Reviewed
• [Journal Article] A Self-supported Palladium-Bipyridyl Catalyst for the Suzuki-Miyaura Coupling in Water (2010)
  • Author(s): Uozumi Y.
  • Journal Title: Heterocycles Volume: 80 Pages: 505-514
  • NAID: 40016900123
  • Peer Reviewed
• [Journal Article] Copper-Free Sonogashira coupling in water with an amphiphilic resin-supported palladium complex (2010)
  • Author(s): Uozumi Y.
  • Journal Title: Tetrahedron Volume: 66 Pages: 1064-1069
  • Peer Reviewed
• [Journal Article] Heterogeneous Aromatic Amination of Aryl Halides with Ariylamines in Water with PS-PEG Resin-Supported Palladium Complexes (2010)
  • Author(s): Uozumi Y.
  • Journal Title: Chem.Asian J. Volume: 5 Pages: 1788-1789
  • Peer Reviewed
• [Journal Article] Green Chemistry-A New Paradigm of Organic Synthesis (2010)
  • Author(s): Uozumi Y.
  • Journal Title: Synlett Pages: 1988-1989
  • Peer Reviewed
• [Journal Article] Palladium Membrane-Installed Microchannel Devices for Instantaneous Suzuki-Miyaura Cross-Coupling (2010)
  • Author(s): Uozumi Y.
  • Journal Title: Chem.Eur.J. Volume: 16 Pages: 11311-11319
  • Peer Reviewed
• [Journal Article] H2O2-Oxidation of Alcohols Promoted by Polymeric Phosphotungstate Catalysts (2010)
  • Author(s): Uozumi Y.
  • Journal Title: Org.Lett. Volume: 12 Pages: 4540-4543
  • Peer Reviewed
• [Presentation] Recent Progress in the Suzuki-Miyaura Coupling : Green, Flow, Asymmetrie Catalytic Systems (2012)
  • Author(s): Uozumi, Y
  • Organizer: 8th CRC International Symposium on Organometallics & Catalysis
  • Place of Presentation: Lecture Theater 206, York University (Canada)(招待講演)
  • Year and Date: 2012-02-04
• [Presentation] 高分子担持Pd触媒を用いた水中有機合成 (2012)
  • Author(s): 魚住泰広
  • Organizer: 有機合成のニュートレンド2012
  • Place of Presentation: エル・おおさか(大阪府)(招待講演)
  • Year and Date: 2012-02-02
• [Presentation] 水中での有機分子変換を実現する高分子担持遷移金属触媒 (2011)
  • Author(s): 魚住泰広
  • Organizer: 第8回触媒相模セミナー
  • Place of Presentation: 東ソー東京センター大会議室(神奈川県)(招待講演)
  • Year and Date: 2011-11-17
• [Presentation] 高分子固定化触媒による不均一水中有機プロセスの開発 (2011)
  • Author(s): 魚住泰広
  • Organizer: グリーン・サステイナブルケミストリー(GSC)講演会
  • Place of Presentation: 産業技術総合研究所会議室(茨城県)(招待講演)
  • Year and Date: 2011-11-08
• [Presentation] Efficient Organic Transformations in Water with Polymer-Supported Transition Metal Catalysits (2011)
  • Author(s): Uozumi, Y
  • Organizer: The 14th Asian Chemical Congress
  • Place of Presentation: The Queen Sirikit National Convention Center (Thailand)(招待講演)
  • Year and Date: 2011-09-08
• [Presentation] Catalytic Organic Transformations in Water (2011)
  • Author(s): Uozumi, Y
  • Organizer: The 14th Asian Chemical Congress
  • Place of Presentation: The Queen Sirikit National Convention Center (Thailand)(招待講演)
  • Year and Date: 2011-09-08
• [Presentation] Water : as a Medium of Organic Transformations (2011)
  • Author(s): Uozumi, Y
  • Organizer: The 14th Asian Chemical Congress
  • Place of Presentation: The Queen Sirikit National Convention Center (Thailand)(招待講演)
  • Year and Date: 2011-09-07
• [Presentation] Heterogeneous catalytic asymmetric synthesis in water with polymeric palladium complexes (2010)
  • Author(s): Yasuhiro Uozumi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ヒルトンホテル(Honolulu, USA)
  • Year and Date: 2010-12-17
• [Presentation] Instantaneous cross-coupling using catalytic membrane-installed microchannel devices (2010)
  • Author(s): Yasuhiro Uozumi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ヒルトンホテル(Honolulu, USA)
  • Year and Date: 2010-12-16
• [Presentation] Asymmetric Suzuki-Miyaura coupling (2010)
  • Author(s): Yasuhiro Uozumi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ヒルトンホテル(Honolulu, USA)
  • Year and Date: 2010-12-15
• [Presentation] 水中での触媒的有機化学合成 (2010)
  • Author(s): 魚住泰広
  • Organizer: 水科学ワークショップ「水を知る、水を活かす、水を創る」
  • Place of Presentation: 理化学研究所(和光市)
  • Year and Date: 2010-12-06
• [Presentation] クリーン有機合成を実現する水中機能性固定化遷移金属触媒 (2010)
  • Author(s): 魚住泰広
  • Organizer: 日本プロセス化学会 2010ウィンターシンポジウム
  • Place of Presentation: ウィンクあいち(名古屋市)
  • Year and Date: 2010-12-03
• [Presentation] Organic Molecular Transformations in Water with Recyclable Transition Metal Catalysts (2010)
  • Author(s): Yasuhiro Uozumi
  • Organizer: McGill-RIKEN Scientific Workshop on Nanotechnology and Green Chemistry
  • Place of Presentation: Hotel du Lac (Quebec, Canada)
  • Year and Date: 2010-09-22
• [Presentation] Organic Molecular Transformations in Water with Recyclable Transition Metal Catalysts (2010)
  • Author(s): Yasuhiro Uozumi
  • Organizer: NIMS 2010 Conference Challenges of Nanomaterials Science : towards the Solution of Environment and Energy Problems
  • Place of Presentation: つくば国際会議場(つくば市)
  • Year and Date: 2010-07-14
• [Presentation] 水中不均一でのPd触媒反応 (2010)
  • Author(s): 魚住泰広
  • Organizer: 第43回有機金属若手の会 夏の学校
  • Place of Presentation: 休暇村 答志島(福岡市)
  • Year and Date: 2010-07-06
• [Presentation] 水中不均一での不斉Pd触媒反応 (2010)
  • Author(s): 魚住泰広
  • Organizer: 第22回万有札幌シンポジウム構築的有機合成化学:医療そして材料科学の未来へ
  • Place of Presentation: さっぽろ芸術文化の館(札幌市)
  • Year and Date: 2010-07-03
• [Presentation] 水中で有機反応は可能か-不均一パラジウム触媒による精密化学変換- (2010)
  • Author(s): 魚住泰広
  • Organizer: 創造機能化学講演会
  • Place of Presentation: 学士会館(東京都)
  • Year and Date: 2010-06-08
• [Remarks]
  • URL: http://www.ims.ac.jp/know/bio/uozumi/uozumi.html
• [Remarks]
  • URL: http://www.ims.ac.jp/know/bio/uozumi/uozumi.html