マイクロリアクター内の微小反応場を活用する電解発生活性種の時間的・空間的制御

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 24106711
• 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: Yokohama National University
• Principal Investigator: 跡部 真人 横浜国立大学, 環境情報研究院, 教授 (90291351)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2013: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2012: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: マイクロリクター / 時間的・空間的制御 / 電解発生活性種 / カスケード反応 / 連続的レドックス反応 / マイクロリアクター

Research Abstract

微小な流路内で化学反応を行うマイクロリアクターは、様々な分野で応用が期待されている反応デバイスであり、これを利用した研究は1990年代初頭から分析化学の分野で、また、最近は有機合成化学の分野でも大きな成果を挙げている。とくに大きな比界面積を有し迅速な溶液混合が可能といった特徴は、均一系反応よりもむしろ固－液不均一系界面での反応のほうが効率化できるなど利点が多く、典型的な固－液界面での反応である電気化学反応においても大変魅力的なものと言える。さらに、電気化学測定・分析の領域のみならず、電解合成の分野においては、マイクロリアクターの利点はこれだけではない。電極間距離がマイクロオーダーであり、「電解液の流れがリアクター内で厳密に制御されている」といった特徴を最大限に活用すれば、従来のバッチ式反応容器（フラスコやビーカー）では決して実現できなかった全く新しい電解合成反応や電解合成システムが構築できることも予想される。このような着想に基づき、平成25年度はマイクロリアクターを利用した「連続的レドックス反応システムの開発」に着手した。具体的には連続的レドックス反応によるハロゲン化フェノール誘導体からのジアリールエーテル合成をモデルに選定し、従来のバッチ式反応容器（フラスコやビーカー）では決して実現できなかった全く新しい電解合成システムが、マイクロリアクターの活用により構築できることを検証した。

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] Sequential Paired Electrosynthesis of a Diaryl Ether Derivative Using an Electrochemical Microreactor (2014)
  • Author(s): Kashiwagi, T.; Fuchigami, T.; Saito, T.; Nishiyama, S.; Atobe, M.
  • Journal Title: Chem. Lett. Volume: 43 Issue: 6 Pages: 799-801
  • DOI: 10.1246/cl.140046
  • NAID: 130004868158
  • Peer Reviewed
• [Journal Article] 電気化学マイクロリアクターを活用する新規有機電解合成プロセスの開発 (2014)
  • Author(s): 柏木恒雄，跡部真人
  • Journal Title: 有機合成化学協会誌 Volume: 72
  • NAID: 130004548601
  • Peer Reviewed
• [Journal Article] Size-controlled Spherical Polymer Nanoparticles: Synthesis with Tandem Acoustic Emulsification Followed by Soap-free Emulsion Polymerization and One-step Fabrication of Colloidal Crystal Films of Various Colors (2014)
  • Author(s): Hirai, Y.; Nakabayashi, K.; Kojima, M.; Atobe, M.
  • Journal Title: Ultrason. Sonochem. Volume: 21 Issue: 6 Pages: 1921-1927
  • DOI: 10.1016/j.ultsonch.2013.12.006
  • Peer Reviewed
• [Journal Article] Reaction Condition Screening by Using Electrochemical Microreactor: Application to Anodic Phenol-arene C,C Cross-Coupling Reaction in High Acceptor Number Media (2013)
  • Author(s): Kashiwagi, T.; Elsilerb, B.; Waldvogel, S. R.; Fuchigami, T.; Atobe, M.
  • Journal Title: J. Electrochem. Soc. Volume: 160 Issue: 7 Pages: G3058-G3061
  • DOI: 10.1149/2.011307jes
  • Peer Reviewed
• [Journal Article] Size-Controlled Synthesis of Polymer Nanoparticles with Tandem Acoustic Emulsification Followed by Soap-Free Emulsion Polymerization (2013)
  • Author(s): Nakabayashi, K.; Kojima, M.; Inagi, S.; Hirai, Y.; Atobe, M.
  • Journal Title: ACS Macro Lett. Volume: 2 Issue: 6 Pages: 482-484
  • DOI: 10.1021/mz4001817
  • Peer Reviewed
• [Journal Article] Tandem Acoustic Emulsion, an Effective Tool for the Electrosynthesis of Highly Transparent and Conductive Polymer Films (2013)
  • Author(s): Nakabayashi, K.; Fuchigami, T.; Atobe, M.
  • Journal Title: Electrochim. Acta Volume: 110 Pages: 593-598
  • DOI: 10.1016/j.electacta.2013.03.120
  • Peer Reviewed
• [Journal Article] Electrochemical and Photoelectrochemical Behaviors of Polythiophene Nanowires Prepared by Templated Electrodeposition in Supercritical Fluids (2013)
  • Author(s): Sakamoto, K.; Nakabayashi, K.; Fuchigami, T.; Atobe, M.
  • Journal Title: Electrochemistry Volume: 81 Issue: 5 Pages: 328-330
  • DOI: 10.5796/electrochemistry.81.328
  • NAID: 10031151991
  • ISSN: 1344-3542, 2186-2451
  • Peer Reviewed
• [Journal Article] Morphological and Electrochemical Properties of 3,4-Substitued Polythiophene Films Prepared by Electrochemical Polymerization (2013)
  • Author(s): Furuta, K.; Koyama, H.; Honma, S.; Nakabayashi, K.; Atobe, M.
  • Journal Title: Electrochemistry Volume: 81 Issue: 5 Pages: 334-336
  • DOI: 10.5796/electrochemistry.81.334
  • NAID: 10031151993
  • ISSN: 1344-3542, 2186-2451
  • Peer Reviewed
• [Journal Article] Preparation of Highly Aligned Arrays of Conducting Polymer Nanowires Using Templated Electropolymerization in Supercritical Fluids (2013)
  • Author(s): Atobe, M.; Yoshida, N.; Sakamoto, K.; Sugino, K.; Fuchigami. T.
  • Journal Title: Electrochim. Acta Volume: 87 Pages: 409-415
  • Peer Reviewed
• [Journal Article] Continuous In Situ Electrogeneration of O-Benzoquinone in Microreactor: Application to High Yield Reaction with Benzenethiols (2013)
  • Author(s): Kashiwagi, T.; Amemiya, F.; Fuchigami, T.; Atobe, M.
  • Journal Title: J. Flow Chem. Volume: 3 Issue: 1 Pages: 17-22
  • DOI: 10.1556/jfc-d-12-00019
  • Peer Reviewed
• [Journal Article] 有機エレクトロニクスへの応用を指向した導電性高分子材料の構造制御型合成 (2013)
  • Author(s): 跡部真人
  • Journal Title: 電気化学および工業物理化学 Volume: 81 Pages: 288-292
• [Journal Article] Electrocatalytic Debromination of Open-Chain and Cyclic Dibromides in Ionic Liquids with Cobalt(II)salen Complex as Mediator (2013)
  • Author(s): Yi Shen, Shinsuke Inagi, Mahito Atobe, Toshio Fuchigami
  • Journal Title: Research on Chemical Intermediates Volume: 39 Issue: 1 Pages: 89-99
  • DOI: 10.1007/s11164-012-0634-6
  • Peer Reviewed
• [Journal Article] Anodic Oxidation on a Boron-Doped Diamond Electrode Mediated by Methoxy Radicals (2012)
  • Author(s): Sumi, T.; Saitoh, T.; Natsui, K.; Yamamoto, T.; Atobe, M.; Einaga, Y.; Nishiyama, S.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 51 Issue: 22 Pages: 5443-5446
  • DOI: 10.1002/anie.201200878
  • Peer Reviewed
• [Journal Article] Electro-Click Modification of Conducting Polymer Surface Using Cu(I) Species Generated on a Bipolar Electrode in a Gradient Manner (2012)
  • Author(s): Naoki Shida
  • Journal Title: ACS Macro Letters Volume: 1 Issue: 6 Pages: 656-659
  • DOI: 10.1021/mz300210w
  • Peer Reviewed
• [Journal Article] In Situ Electro generation of o-Benzoquinone and High Yield Reaction with Benzenethiols in a Micro flow System (2012)
  • Author(s): Tsuneo KASHIWAGI, Fumihiro AMEMIYA, Toshio FUCHIGAMI, Mahito ATOBE
  • Journal Title: Chem. Commun Volume: 48 Issue: 22 Pages: 2806-2808
  • DOI: 10.1039/c2cc17979b
  • Peer Reviewed
• [Journal Article] タンデム式超音波乳化法を利用する分散剤フリーナノエマルション溶液の創成とその応用 (2012)
  • Author(s): 跡部真人
  • Journal Title: オレオサイエンス Volume: 12（6） Pages: 233-239
  • NAID: 130004853429
• [Presentation] 超音波乳化を利用する分散剤フリーなナノエマルション溶液の創製とポリマー材料合成への応用 (2014)
  • Author(s): 跡部真人
  • Organizer: 反応性・機能性材料シンポジウム
  • Place of Presentation: 横浜
  • Invited
• [Presentation] Electrochemical Synthesis of Monodisperse Oligothiophene Using a Flow Microreactor (2013)
  • Author(s): Atobe, M.
  • Organizer: The 8th International Symposium on Integrated Synthesis
  • Place of Presentation: Kyoto
  • Invited
• [Presentation] Preparation of a Highly Clear and Transparent Nanoemulsion Using Tandem Acoustic Emulsification: Application to Chemical and Electrochemical Polymerization (2013)
  • Author(s): Atobe, M.
  • Organizer: 11st International Symposium on Organic Reactions
  • Place of Presentation: Taipei, Taiwan
  • Invited
• [Presentation] Preparation of a Highly Clear and Transparent Nanoemulsion under Surfactant-Free Conditions Using Tandem Acoustic Emulsification: Application to Chemical and Electrochemical Polymerization (2013)
  • Author(s): Atobe, M.; Nakabayashi, K.; Kojima, M.; Hirai, Y.
  • Organizer: 1st Meeting of the Asia-Oceania Sonochemical Society
  • Place of Presentation: Melbourne, Australia
  • Invited
• [Presentation] 有機電気化学入門講座 ～基礎原理から新手法まで～ (2013)
  • Author(s): 跡部真人
  • Organizer: RDセミナー
  • Place of Presentation: 東京
  • Invited
• [Presentation] Controlling and Improvement of Electrosynthetic Electrochemical Microreactor Reaction by Using Microreactor: Application to Intermolecular Coupling Reaction of Phenol Derivatives (2012)
  • Author(s): Kashiwagi, T.; Waldvogel, S. R.; Atobe, M.
  • Organizer: PRIME 2012
  • Place of Presentation: ホノルル（アメリカ合衆国）
  • Year and Date: 2012-10-12
• [Presentation] Preparation of Nanoemulsion Using Tandem Acoustic Emulsification and Its Application to Templated Electropolymerization (2012)
  • Author(s): Nakabayashi, K.; Fuchigami, T.; Atobe, M.
  • Organizer: PRIME 2012
  • Place of Presentation: ホノルル（アメリカ合衆国）
  • Year and Date: 2012-10-12
• [Presentation] Anodic Phenol Coupling Reaction Using Electrochemical Microreactor (2012)
  • Author(s): Kashiwagi, T.; Waldvogel, S. R.; Atobe, M.
  • Organizer: 63rd Annual Meeting of the Internetional Society of Electrochemistry
  • Place of Presentation: プラハ（アメリカ合衆国）
  • Year and Date: 2012-08-19
• [Presentation] Preparation of Transparent Nano-emulsion Using Tandem Acoustic Emulsification and Its Application to Electropolymerization (2012)
  • Author(s): Nakabayashi, K.; Fuchigami, T.; Atobe, M.
  • Organizer: 63rd Annual Meeting of the Internetional Society of Electrochemistry
  • Place of Presentation: プラハ（チェコ共和国）
  • Year and Date: 2012-08-19
• [Presentation] Preparation of EDOT monomer nanoemulsions using tandem acoustic emulsificatio nand their application to template electrochemical polymerization (2012)
  • Author(s): Nakabayashi, K.; Fuchigami, T.; Atobe, M.
  • Organizer: 3rd German-Japanese Symposium on Electrosynthesis
  • Place of Presentation: マインツ（ドイツ連邦共和国）
  • Year and Date: 2012-08-16
• [Presentation] Anodic Phenol-Arene C,C Cross-Coupling Reaction in High Acceptor Number Media (2012)
  • Author(s): Kashiwagi, T.; Waldvogel, S. R.; Atobe, M.
  • Organizer: 3rd German-Japanese Symposium on Electrosynthesis
  • Place of Presentation: マインツ（ドイツ連邦共和国）
  • Year and Date: 2012-08-16
• [Presentation] Anodic Oxidation on a Boron-Doped Diamond Electrode (2012)
  • Author(s): Sumi, T.; Saitoh, T.; Natsui, K.; Yamamoto, T.; Atobe, M.; Einaga, Y.; Nishiyama, S.
  • Organizer: 3rd German-Japanese Symposium on Electrosynthesis
  • Place of Presentation: マインツ（ドイツ連邦共和国）
  • Year and Date: 2012-08-16
• [Presentation] Preparation of a Highly Clear and Transparent Nanoemulsion under Surfactant-Free Conditions Using Tandem Acoustic Emulsification and Its Application to Electropolymerization (2012)
  • Author(s): Atobe, M. Nakabayashi, K.; Fuchigami, T.; Machida, K.; Takeda, S.; Tamamitsu, K.
  • Organizer: 221st Meeting on The Electrochemical Society
  • Place of Presentation: シアトル（アメリカ合衆国）
  • Year and Date: 2012-05-06
• [Presentation] 導電性高分子材料の形状制御型合成とその応用 (2012)
  • Author(s): 跡部真人
  • Organizer: 電気化学会キャパシタ技術委員会 第３回研究会（講演会）
  • Place of Presentation: 東京
  • Invited
• [Book] Electrosynthesis in Supercritical Fluids, Encyclopedia of Applied Electrochemistry (2014)
  • Author(s): Atobe, M.
  • Publisher: Springer
• [Book] Electrosynthesis under Ultrasound and Centrifugal Fields, Encyclopedia of Applied Electrochemistry (2014)
  • Author(s): Atobe, M.
  • Publisher: Springer
• [Book] 電解反応, フロー・マイクロ合成 (2014)
  • Author(s): 跡部真人
  • Total Pages: 12
  • Publisher: 化学同人
• [Book] Structure Control Synthesis of Polyeniline Materials Using Electrochemical and Chemical Polymerizations in Unique Reaction Fields and Media, Trends in Polyaniline Research (2013)
  • Author(s): Atobe, M.
  • Total Pages: 14
  • Publisher: Nova Science Publishers
• [Book] 有機電気化学, 電気化学便覧 第6版 (2013)
  • Author(s): 跡部真人
  • Total Pages: 27
  • Publisher: 丸善
• [Book] 有機電解合成, 電気化学便覧 第6版 (2013)
  • Author(s): 跡部真人
  • Total Pages: 6
  • Publisher: 丸善
• [Book] 有機電気化学 (2012)
  • Author(s): 淵上寿雄, 跡部真人, 稲木信介
  • Total Pages: 193
  • Publisher: コロナ社
• [Remarks] Atobe Laboratory
  • URL: http://www.atobe-lab.ynu.ac.jp/
• [Remarks] 横浜国立大学大学院環境情報研究院 跡部研究室ホームページ
  • URL: http://www.atobe-lab.ynu.ac.jp