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: 24106744
• 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): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥7,150,000 (Direct Cost: ¥5,500,000、Indirect Cost: ¥1,650,000); Fiscal Year 2013: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2012: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: マイクロリアクター / 固定化触媒 / 高速化触媒 / フリー・リアクタ / 膜触媒 / フロー・リアクタ

Research Abstract

本報告者は前年度までに (A) 触媒活性高分子膜をマイクロ流路内に２液系層流を発生させ，また同膜状高分子マトリクス内でのナノ金属粒子を発生・調製；(B) これら触媒膜導入マイクロ流路デバイスを用いハロベンゼン類の水素化脱ハロゲン化反応をギ酸を水素源として達成；(C) イミダゾール残基を配位基とするポリアクリロアミドと各種金属（Pd, Cu, など）との配位結合架橋に依る不溶性高分子触媒創成を達成してきた。本年度は独自に開発してきた両親媒高分子担持 Pt ナノ粒子触媒をカートリッジ化し，「固／液／気」３相系反応を実行しえる連続フロー反応装置に適用することで，アルコール類の酸素酸化触媒反応を実践的なレベルへと展開した。完成した連続フロー酸素酸化システムは各種アルコール類に有効で，多様なのカルボン酸（１級アルコール原料）ケトン（２級アルコール原料）を高収率で与えた。
またフェノールスルホン酸とホルムアルデヒドの縮合ポリマーを高分子ブレンステッド酸触媒として脱水縮合エステル化反応に適用した。開発した高分子ブレンステッド酸触媒は他の代表的高分子触媒よりも圧倒的にエステル化活性が高いのみならず，有機芳香族スルホン酸触媒（均一系条件）との比較においてさえも，むしろ高活性であることが見いだされた。本高分子触媒をカートリッジ化しオレイン酸とメタノールの直接エステル化によるバイオディーゼル燃料エステルの連続フロー合成へと展開した。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Hybrid of Palladium Nanoparticles and Silicon Nanowire Ar-ray: A Platform for Catalytic Heterogeneous Reactions (2014)
  • Author(s): Yamada Y.A.M, Yuyama Y, Sato T, Fujikawa S, Uozumi Y
  • Journal Title: Angew. Chem. Int. Ed Volume: 53 Issue: 1 Pages: 127-131
  • DOI: 10.1002/anie.201308541
  • Peer Reviewed
• [Journal Article] Polymeric Bimetallic Catalyst-Promoted In-Water Dehydrative Alkylation of Ammonia and Amines with Alcohols (2013)
  • Author(s): Yamada M.A.Y, Ohta H, Yuyama Y, Uozumi Y
  • Journal Title: Synthesis Volume: 45 Issue: 15 Pages: 2093-2100
  • DOI: 10.1055/s-0033-1338797
  • Peer Reviewed
• [Journal Article] Highly Efficient Iron(0) Nanoparticle-Catalyzed Hydrogenation in Water in Flow (2013)
  • Author(s): Hudson R, Hamasaka G, Osako T, Yamada M.A.Y, Li C.-J, Uozumi Y, Moores A
  • Journal Title: Green Chem. Volume: 15 Issue: 8 Pages: 2141-2148
  • DOI: 10.1039/c3gc40789f
  • Peer Reviewed
• [Journal Article] Asymmetric Sonogashira Coupling with a Chiral Palladium Imidazoindole Phosphine Complex (2013)
  • Author(s): Zhou H, Uozumi Y
  • Journal Title: Synlett Volume: 24 Issue: 19 Pages: 2550-2554
  • DOI: 10.1055/s-0033-1339873
  • Peer Reviewed
• [Journal Article] Direct Dehydrative Esterification of Alcohols and Carboxylic Acids with a Macroporous Polymeric Acid Catalyst (2013)
  • Author(s): Minakawa M, Baek H, Yamada Y.M.A, Han J, Uozumi Y
  • Journal Title: Org. Lett. Volume: 15 Pages: 5798-5801
  • Peer Reviewed
• [Journal Article] An Amphiphilic Self-Assembled Polymeric Copper Catalyst at Ppm Level: Click Chemistry (2012)
  • Author(s): Y. M. A. Yamada, S. M. Sarkar, and Y. Uozumi
  • Journal Title: J. Am. Chem. Soc Volume: 134 Issue: 22 Pages: 9285-9290
  • DOI: 10.1021/ja3036543
  • Peer Reviewed
• [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] Enantioselctive Carbenoid Insertion into Phenolic O-H Bonds with a Chiral Copper(I) Imidazoindolephosphine Complex (2012)
  • Author(s): Yasuhiro Uozumi
  • Journal Title: Org. Lett. Volume: 14 Issue: 1 Pages: 194-197
  • DOI: 10.1021/ol202977j
  • Peer Reviewed
• [Journal Article] Development of Polymeric Pd Nanoparticle Membrane-Installed Microflow Devices and Their Application in Hydrodehalogenation (2012)
  • Author(s): Y. M. A. Yamada, T. Watanabe, A. Ohno, and Y. Uozumi
  • Journal Title: ChemSusChem Volume: 5 Issue: 2 Pages: 293-299
  • DOI: 10.1002/cssc.201100418
  • Peer Reviewed
• [Presentation] グリーン化学合成研究の最先端 (2013)
  • Author(s): 魚住泰広
  • Organizer: 第14回自然科学研究機構シンポジウム 分子が拓くグリーン未来
  • Place of Presentation: 学術総合センター（東京都）
  • Year and Date: 2013-03-20
  • Invited
• [Presentation] Development of Heterogeneous Catalysis toward Ideal Chemical Processes (2013)
  • Author(s): Yasuhiro Uozumi
  • Organizer: 3rd IMS-CHIMIE PARISTECH Joint Symposium
  • Place of Presentation: 岡崎コンファレンスセンター（愛知県）
  • Year and Date: 2013-02-12
  • Invited
• [Presentation] Molecular Architecture-Based Administration of Catalysis in Water via Self-Assembly of Amphiphilic Pincer Complexes (2013)
  • Author(s): Yasuhiro UOzumi
  • Organizer: 2013 Asian Core Winter School
  • Place of Presentation: Hanwha Resort Haeundae(Korea)
  • Year and Date: 2013-01-29
  • Invited
• [Presentation] Amphiphilic Self-Assembled Polymeric Pd and Cu Catalysts: Suzuki-Miyaura Coupling and Huisgen Cycloaddition at ppm Levels (2012)
  • Author(s): Yasuhiro Uozumi
  • Organizer: The 2nd Korea Forum on Organic Chemistry
  • Place of Presentation: Seoul National University(Korea)
  • Year and Date: 2012-11-23
  • Invited
• [Presentation] 遷移金属不斉触媒の革新と展開 (2012)
  • Author(s): 魚住泰広
  • Organizer: 第２回ＣＳＪ化学フェスタ2012
  • Place of Presentation: 東京工業大学（東京都）
  • Year and Date: 2012-10-15
  • Invited
• [Presentation] Amphiphilic Self-Assembled Polymeric Pd and Cu Catalysts: Suzuki-Miyaura Coupling and Huisgen Cycloaddition at ppm Levels (2012)
  • Author(s): Yasuhiro Uozumi
  • Organizer: The 6th CMDS Meeting on OMCOS 2012
  • Place of Presentation: Kensington Star Hotel(Korea)
  • Year and Date: 2012-09-12
  • Invited
• [Presentation] NCN Pincer Palladium Complexes-Their Preparation via a Ligand Introduction Route and Their Catalytic Properties (2012)
  • Author(s): Yasuhiro Uozumi
  • Organizer: Seminar at Faculty of Chemistry, Weizmann Institute of Science
  • Place of Presentation: Weizmann Institute of Science(Israel)
  • Year and Date: 2012-04-03
  • Invited
• [Presentation] Molecular Architecture-Based Administration of Catalysis in Water via Self-Assembly of an Amphiphilic Pincer Complexes
  • Author(s): Yasuhiro Uozumi
  • Organizer: 96th Canadian Chemistry Conference and Exhibition
  • Place of Presentation: Quebec City Convention Center(Canada)
  • Invited
• [Presentation] 化学と酒
  • Author(s): 魚住泰広
  • Organizer: 日本化学会秋季事業 第3回CSJ化学フェスタ2013
  • Place of Presentation: タワーホール船橋（東京都）
  • Invited
• [Presentation] Development of Silicon Nanowire Array as A Platform for Catalytic Heterogeneous Reactions
  • Author(s): Yasuhiro Uozumi
  • Organizer: Asian Core Winter School on Frontiers of Molecular, Photo-and Material Sciences
  • Place of Presentation: Institute of Atomic and Molecular Sciences(Taiwan)
  • Invited
• [Presentation] 両親媒性高分子反応場：「雨宿り効果」に立脚する反応駆動システム
  • Author(s): 魚住泰広
  • Organizer: 第11回岡山理科大学グリーン元素科学シンポジウム
  • Place of Presentation: 岡山理科大学（岡山県）
  • Invited
• [Presentation] Amphiphilic Polymeric Reaction Environment: Reaction Driving Based on the "Umbrella Effect"
  • Author(s): Yasuhiro Uozumi
  • Organizer: 京都大学化学研究所 国際シンポジウムICRIS'14
  • Place of Presentation: 京都大学（京都市）
  • Invited
• [Book] Comprehensive Chirality (2012)
  • Author(s): Yasuhiro Uozumi
  • Publisher: Elsevier
• [Book] Science of Synthesis: Water in Organic Synthesis (2012)
  • Author(s): Yasuhiro Uozumi
  • Publisher: Thieme
• [Remarks] 分子科学研究所 錯体触媒研究部門ホームページ
• [Remarks] http://www.ims.ac.jp/know/bio/uozumi/uozumi.html