活性種の時空間制御が可能なフロー電解反応を基軸とする多段階連続反応システムの創製

• Project/Area Number: 20H02513
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 27020:Chemical reaction and process system engineering-related
• Research Institution: Yokohama National University
• Principal Investigator: 跡部 真人 横浜国立大学, 大学院工学研究院, 教授 (90291351)
• Project Period (FY): 2020-04-01 – 2024-03-31
• Project Status: Granted (Fiscal Year 2023)
• Budget Amount: ¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000); Fiscal Year 2023: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2022: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2021: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2020: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
• Keywords: フロー電解 / 多段階連続反応 / 活性種 / 時空間制御 / フローマイクロリアクター / 有機電解反応 / 電解発生活性種

Outline of Research at the Start

マイクロフロー技術は、これまで反応に用いることが難しかった化学種を制御、利用できる可能性を秘めており、これによる多段階連続反応システムの開発が注目されている。
本研究課題では電気化学的に発生させた活性種・中間体あるいは不安定な電解反応基質をマイクロフロー技術により時間的・空間的に制御し、これを利用することで、従来法では決して実現できない全く新しい高効率・高選択的な多段階連続反応システムを創製する。

Outline of Annual Research Achievements

本研究では、グリーン・サスティナブルケミストリーの一翼を担うことが期待される有機電解プロセスの高効率化、高選択化、高度制御化を指向し、「有機電解反応」と「マイクロフロー技術」との融合を推し進める。特に反応場が微小空間であるマイクロリアクターの特徴を最大限に利用し、電気化学的に発生させた高活性種あるいは不安定な基質や中間体を時間的・空間的に制御することで、従来法では決して実現できない全く新しい高効率・高選択的な多段階連続反応システムの創製を目指すことを目的とする。
2022年度は、プレ化学反応により発生させた不安定化学種を分解あるいは副反応を起こす前に速やかに所望の後続電解反応に導く新規連続フロー合成プロセスの構築に着手した。
具体的な検討事項として、各種アルデヒドとアミンの効率的なプレ脱水反応過程を実現するフロー型脱水カラムシステムを開発した。ここでは、性状も含めた最適な脱水剤（モレキューラーシーブ、MgSO4、Na2SO4など）の選定とカラム寸法（内径、カラム長）、流速などの最適化を行い、効率的なイミン生成のための条件を整えた。

Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

2022年度に予定されていた研究項目「2）プレ化学反応で発生させた不安定化学種を基質とするフロー電解反応」について、各種アルデヒドとアミンの効率的なプレ脱水反応過程を実現するフロー型脱水カラムシステムを開発することに成功した。

Strategy for Future Research Activity

引き続き、今後はプレ化学反応により発生させた不安定化学種を分解あるいは副反応を起こす前に速やかに所望の後続電解反応に導く新規連続フロー合成プロセスの構築に従事する。
具体的な検討事項として、各種アルデヒドとアミンの効率的なプレ脱水反応過程により生じるイミン、とりわけ、脂肪族アルデヒドを基質とした場合に発生する不安定イミンを即座に後続の電解カルボキシル化に供することで新規なアミノ酸合成にチャレンジする。

Research Products

• [Journal Article] β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations (2023)
  • Author(s): IZUMIYA Rumi、ATOBE Mahito、SHIDA Naoki
  • Journal Title: Electrochemistry Volume: 91 Issue: 11 Pages: 112003-112003
  • DOI: 10.5796/electrochemistry.23-67010
  • ISSN: 1344-3542, 2186-2451
  • Year and Date: 2023-11-28
  • Peer Reviewed / Open Access
• [Journal Article] Susceptibility of Polycyclic Aromatic Hydrocarbons in Oxidative Voltammetry: Unveiling the Effect of Electrolyte-coordination (2023)
  • Author(s): YOSHINAGA Shohei、ATOBE Mahito、SHIDA Naoki
  • Journal Title: Electrochemistry Volume: 91 Issue: 11 Pages: 112002-112002
  • DOI: 10.5796/electrochemistry.23-67013
  • ISSN: 1344-3542, 2186-2451
  • Year and Date: 2023-11-28
  • Peer Reviewed / Open Access
• [Journal Article] Diastereoselective Electrocatalytic Hydrogenation of Cyclic Ketones Using a Proton-Exchange Membrane Reactor: A Step toward the Electrification of Fine-Chemical Production (2023)
  • Author(s): Shimizu Yugo、Harada Juri、Fukazawa Atsushi、Suzuki Tomohiro、Kondo Junko N.、Shida Naoki、Atobe Mahito
  • Journal Title: ACS Energy Letters Volume: 8 Issue: 2 Pages: 1010-1017
  • DOI: 10.1021/acsenergylett.2c02573
  • Peer Reviewed
• [Journal Article] Comparative Investigation of Electrocatalytic Oxidation of Cyclohexene by Proton-Exchange Membrane and Anion-Exchange Membrane Electrolyzers (2022)
  • Author(s): Shida Naoki、Atobe Mahito、Ido Yuto、Shimizu Yugo
  • Journal Title: Synthesis Volume: 55 Issue: 18 Pages: 2979-2984
  • DOI: 10.1055/a-2000-8231
  • Peer Reviewed
• [Journal Article] Pd?H Species on Electrode Stabilized by Solvent Co-Adsorption: Observation by Operando IR Spectroscopy (2022)
  • Author(s): Kondo Junko N.、Ge Shuo、Suzuki Tomohiro、Osuga Ryota、Matsumoto Takeshi、Yokoi Toshiyuki、Shimizu Yugo、Fukazawa Atsushi、Shida Naoki、Atobe Mahito
  • Journal Title: The Journal of Physical Chemistry C Volume: 126 Issue: 45 Pages: 19376-19385
  • DOI: 10.1021/acs.jpcc.2c05127
  • Peer Reviewed
• [Journal Article] Designing Modular Assembly of Electrochemical Flow Microreactor as an Enabling Technology of Electrosynthesis in Laminar Flow (2022)
  • Author(s): Yata Ayano、Nakamura Yuto、Okamoto Kazuhiro、Shida Naoki、Atobe Mahito
  • Journal Title: European Journal of Organic Chemistry Volume: 2022 Issue: 45
  • DOI: 10.1002/ejoc.202200980
  • Peer Reviewed
• [Journal Article] Mechanistic Insights into the Electrocatalytic Hydrogenation of Alkynes on Pt?Pd Electrocatalysts in a Proton-Exchange Membrane Reactor (2022)
  • Author(s): Nogami Shuji、Shida Naoki、Iguchi Shoji、Nagasawa Kensaku、Inoue Hideo、Yamanaka Ichiro、Mitsushima Shigenori、Atobe Mahito
  • Journal Title: ACS Catalysis Volume: 12 Issue: 9 Pages: 5430-5440
  • DOI: 10.1021/acscatal.2c01594
  • Peer Reviewed
• [Journal Article] カーボンニュートラル実現に向けたキーテクノロジー ―固体高分子電解質電解技術を活用する有機電解 プロセス― (2022)
  • Author(s): 跡部真人
  • Journal Title: 化学 Volume: 77 (10) Pages: 66-67
• [Journal Article] Integrated Flow Emulsion Electrosynthetic System by In Situ Generation of Emulsions, Subsequent Emulsion Electrolysis, and Final Phase Separation (2022)
  • Author(s): Mikami Rio、Shida Naoki、Atobe Mahito
  • Journal Title: Organic Process Research & Development Volume: 21 Issue: 4 Pages: 1268-1278
  • DOI: 10.1021/acs.oprd.2c00004
  • Peer Reviewed
• [Journal Article] Synthesis of piperidine and pyrrolidine derivatives by electroreductive cyclization of imine with terminal dihaloalkanes in a flow microreactor (2022)
  • Author(s): Naito Yuki、Shida Naoki、Atobe Mahito
  • Journal Title: Beilstein Journal of Organic Chemistry Volume: 18 Pages: 350-359
  • DOI: 10.3762/bjoc.18.39
  • Peer Reviewed / Open Access
• [Journal Article] Bayesian optimization with constraint on passed charge for multiparameter screening of electrochemical reductive carboxylation in a flow microreactor (2022)
  • Author(s): Naito Yuki、Kondo Masaru、Nakamura Yuto、Shida Naoki、Ishikawa Kazunori、Washio Takashi、Takizawa Shinobu、Atobe Mahito
  • Journal Title: Chemical Communications Volume: 58 Issue: 24 Pages: 3893-3896
  • DOI: 10.1039/d2cc00124a
  • Peer Reviewed
• [Journal Article] Investigation of Parameter Control for Electrocatalytic Semihydrogenation in a Proton-Exchange Membrane Reactor Utilizing Bayesian Optimization (2022)
  • Author(s): Ashikari Yosuke、Tamaki Takashi、Takahashi Yusuke、Yao Yiyue、Atobe Mahito、Nagaki Aiichiro
  • Journal Title: Frontiers in Chemical Engineering Volume: 3 Pages: 819752-819752
  • DOI: 10.3389/fceng.2021.819752
  • Peer Reviewed / Open Access
• [Journal Article] Electrochemical Trimerization of Catechol to 2,3,6,7,10,11-Hexahydroxytriphenylene Using a Flow Microreactor (2021)
  • Author(s): NAKAMURA Yuto、SATO Yasushi、SHIDA Naoki、ATOBE Mahito
  • Journal Title: Electrochemistry Volume: 89 Issue: 4 Pages: 395-399
  • DOI: 10.5796/electrochemistry.21-00053
  • NAID: 130008062334
  • ISSN: 1344-3542, 2186-2451
  • Year and Date: 2021-07-05
  • Peer Reviewed / Open Access
• [Journal Article] Triple‐phase Boundary in Anion‐Exchange Membrane Reactor Enables Selective Electrosynthesis of Aldehyde from Primary Alcohol (2021)
  • Author(s): Ido Yuto、Fukazawa Atsushi、Furutani Yuka、Sato Yasushi、Shida Naoki、Atobe Mahito
  • Journal Title: ChemSusChem Volume: 14 Issue: 24 Pages: 5405-5409
  • DOI: 10.1002/cssc.202102076
  • Peer Reviewed
• [Journal Article] Anodic substitution reaction of carbamates in a flow microreactor using a stable emulsion solution (2021)
  • Author(s): Mikami Rio、Nakamura Yuto、Shida Naoki、Atobe Mahito
  • Journal Title: Reaction Chemistry and Engineering Volume: 6 Issue: 11 Pages: 2024-2028
  • DOI: 10.1039/d1re00403d
  • Peer Reviewed
• [Journal Article] Electrocatalytic hydrogenation of benzoic acids in a proton-exchange membrane reactor (2021)
  • Author(s): Fukazawa Atsushi、Shimizu Yugo、Shida Naoki、Atobe Mahito
  • Journal Title: Organic and Biomolecular Chemistry Volume: 19 Issue: 34 Pages: 7363-7368
  • DOI: 10.1039/d1ob01197a
  • Peer Reviewed
• [Journal Article] Integrated Flow Synthesis of α-Amino Acids by <i>In Situ</i> Generation of Aldimines and Subsequent Electrochemical Carboxylation (2021)
  • Author(s): Naito Yuki、Nakamura Yuto、Shida Naoki、Senboku Hisanori、Tanaka Kenta、Atobe Mahito
  • Journal Title: The Journal of Organic Chemistry Volume: 86 Issue: 22 Pages: 15953-15960
  • DOI: 10.1021/acs.joc.1c00821
  • Peer Reviewed
• [Journal Article] Electrolytic oxidation of 1H-1,2,4-triazole, 3-amino-1,2,4-triazole, and 4-amino-1,2,4-triazole for energetic material synthesis (2021)
  • Author(s): Mori Kanae、Kumasaki Mieko、Atobe Mahito
  • Journal Title: Science and Technology of Energetic Materials Volume: 82 Issue: 2 Pages: 44-49
  • DOI: 10.34571/stem.82.2_44
  • NAID: 130008037386
  • ISSN: 0368-5977, 1347-9466, 2434-6322
  • Peer Reviewed
• [Journal Article] Electrosynthesis in Laminar Flow Using a Flow Microreactor (2021)
  • Author(s): Shida Naoki、Nakamura Yuto、Atobe Mahito
  • Journal Title: The Chemical Record Volume: 21 Issue: 9 Pages: 2164-2177
  • DOI: 10.1002/tcr.202100016
  • Peer Reviewed
• [Journal Article] Au-catalyzed electrochemical oxidation of alcohols using an electrochemical column flow cell (2021)
  • Author(s): Suga Tatsuya、Shida Naoki、Atobe Mahito
  • Journal Title: Electrochemistry Communications Volume: 124 Pages: 106944-106944
  • DOI: 10.1016/j.elecom.2021.106944
  • Peer Reviewed / Open Access
• [Journal Article] Electrochemical Synthesis of Porous Polypyrrole Materials Using Polyacrylonitrile Monolith Template (2020)
  • Author(s): Kaneda Chinami、Tanaka Kenta、Atobe Mahito
  • Journal Title: KAGAKU KOGAKU RONBUNSHU Volume: 46 Issue: 4 Pages: 129-133
  • DOI: 10.1252/kakoronbunshu.46.129
  • NAID: 130007878349
  • ISSN: 0386-216X, 1349-9203
  • Year and Date: 2020-07-20
  • Peer Reviewed
• [Journal Article] Flow Electrosynthesis and Molecular Weight Control of Polyphenylene Deriving from 1,4-Bis(trimethylsilyl)benzene: Effect of a Silyl Substituent on the Coupling Position (2020)
  • Author(s): NAKAMURA Yuto、TANAKA Kenta、MATSUMURA Yoshimasa、ATOBE Mahito
  • Journal Title: Electrochemistry Volume: 88 Issue: 4 Pages: 336-339
  • DOI: 10.5796/electrochemistry.20-00060
  • NAID: 130007869357
  • ISSN: 1344-3542, 2186-2451
  • Year and Date: 2020-07-05
  • Peer Reviewed / Open Access
• [Journal Article] Highly Selective and Efficient Electrocatalytic Semihydrogenation of Diphenylacetylene in a PEM Reactor with Pt?Pd Alloy Cathode Catalysts (2020)
  • Author(s): Nogami Shuji、Nagasawa Kensaku、Fukazawa Atsushi、Tanaka Kenta、Mitsushima Shigenori、Atobe Mahito
  • Journal Title: Journal of The Electrochemical Society Volume: 167 Issue: 15 Pages: 155506-155506
  • DOI: 10.1149/1945-7111/abaae7
  • Peer Reviewed / Open Access
• [Journal Article] Electrocatalytic asymmetric hydrogenation of α,β-unsaturated acids in a PEM reactor with cinchona-modified palladium catalysts (2020)
  • Author(s): Fukazawa Atsushi、Tanaka Kenta、Hashimoto Yasushi、Sato Yasushi、Atobe Mahito
  • Journal Title: Electrochemistry Communications Volume: 115 Pages: 106734-106734
  • DOI: 10.1016/j.elecom.2020.106734
  • Peer Reviewed
• [Presentation] フローリアクターが革新する新たな有機電解プロセス (2023)
  • Author(s): 跡部真人
  • Organizer: 第７回FlowSTシンポジウム
  • Invited
• [Presentation] フローリアクターが革新する新たな有機電解合成プロセス (2022)
  • Author(s): 跡部真人
  • Organizer: 2022 年度有機合成化学講習会
  • Invited
• [Presentation] Organic Electrosyntheses Using a Proton Exchange Membrane (PEM) Reactor (2022)
  • Author(s): Mahito Atobe
  • Organizer: International Symposium on Innovative Reactions through Controlling Electrons (ISIRCE)
  • Int'l Joint Research / Invited
• [Presentation] Integrated Flow Emulsion Electrosynthetic System for Oxidation of Hydrophobic Amines (2022)
  • Author(s): Mahito Atobe, Rio Mikami, Naoki Shida
  • Organizer: The 15th International Symposium on Organic Reactions (ISOR-15)
  • Int'l Joint Research / Invited
• [Presentation] Electrochemical C-N Coupling Reaction Mediated by π-Extended Iodoarene Catalyst (2022)
  • Author(s): Naoki Shida, Shohei Yoshinaga, Mahito Atobe
  • Organizer: 9th German-Japanese Symposium on Electrosynthesis
  • Int'l Joint Research
• [Presentation] Bayesian Optimization for Multiparameter Screening of Electrosynthetic Processes in a Flow Microreactor (2022)
  • Author(s): Yuto Nakamura, Yuki Naito, Kazuhiro Okamoto, Naoki Shida, Mahito Atobe
  • Organizer: 9th German-Japanese Symposium on Electrosynthesis
  • Int'l Joint Research
• [Presentation] Development of Integrated Flow Emulsion Electrosynthetic System for Oxidation of Hydrophobic Amines (2022)
  • Author(s): Mahito Atobe, Rio Mikami, Naoki Shida
  • Organizer: 9th German-Japanese Symposium on Electrosynthesis
  • Int'l Joint Research
• [Presentation] Development of Integrated Flow Emulsion Electrosynthetic System (2022)
  • Author(s): Mahito Atobe, Rio Mikami, Naoki Shida
  • Organizer: 17th Meeting of the European Society of Sonochemistry
  • Int'l Joint Research / Invited
• [Presentation] 固体高分子電解質（SPE）電解技術が革新する有機電解合成プロセス (2022)
  • Author(s): 跡部真人
  • Organizer: 第30回グリーンケミストリーフォーラム
  • Invited
• [Presentation] Anodic Substitution Reaction of Carbamates in a Flow Microreactor Using a Tandem Acoustic Emulsified Solution (2021)
  • Author(s): Rio Mikami, Yuto Nakamura, Naoki Shida, Mahito Atobe
  • Organizer: ESS-JSS-AOSS 1st Joint Sonochemistry Conference
  • Int'l Joint Research
• [Presentation] Organic Electrosynthetic Reactions Using a Proton-Exchange Membrane (PEM) Reactor (2021)
  • Author(s): Mahito Atobe, Atsushi Fukazawa, Naoki Shida
  • Organizer: 72nd ISE Annual Meeting
  • Int'l Joint Research / Invited
• [Presentation] Electrocatalytic Nuclear Hydrogenation of Benzoic Acids in a Proton Exchange Membrane Reactor (2021)
  • Author(s): Mahito Atobe, Atsushi Fukazawa, Naoki Shida
  • Organizer: 239th ECS Meeting
  • Int'l Joint Research
• [Presentation] フローリアクターが革新する 有機電解合成プロセス (2021)
  • Author(s): 跡部真人
  • Organizer: 近畿化学協会第89回フロー・マイクロ研究会
  • Invited
• [Presentation] リアクターが革新する有機電解プロセス (2020)
  • Author(s): 跡部真人
  • Organizer: 第126回触媒討論会
  • Invited
• [Presentation] Comparative Investigation of Electrocatalytic Oxidation by Proton-Exchange-Membrane and Anion-Exchange-Membrane Electrolyses (2020)
  • Author(s): Yuto Ido, Yutaro Shimizu, Juri Minoshima, Atsushi Fukazawa, Kenta Tanaka, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Highly Efficient Electrochemical Oxidation of Alcohols in a Flow Electrochemical Column Cell Modified with Au Nanoparticle Catalyst (2020)
  • Author(s): Suga Tatsuya, Kenta Tanaka, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Anodic Trimerization of Catechol to Hexahydroxytriphenylene Using a Flow microreactor (2020)
  • Author(s): Yuto Nakamura, Kenta Tanaka, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Highly Selective and Efficient Electrocatalytic Semihydrogenation of Diphenylacetylene to Z-Stilbene Using Pt-Pd Alloy Cathode Catalyst (2020)
  • Author(s): Shuji Nogami, Juri Minoshima, Atsushi Fukazawa, Kensaku Nagasawa, Shigenori Mitsushima, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Continuous Flow Synthesis of N-Phenylphenylglycine by Dehydration and Electrochemical Carboxylation (2020)
  • Author(s): Yuki Naito, Kenta Tanaka, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Anodic Substitution Reaction of Cyclic Carbamates in Stable Nanoemulsion Solution Using a Flow Microreactor (2020)
  • Author(s): Rio Mikami, Yuto Nakamura, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Electrocatalytic Asymmetric Hydrogenation of α,β-Unsaturated Acids in a Proton Exchange Membrane Reactor with Palladium-cinchona Catalysts (2020)
  • Author(s): Atsushi Fukazawa, Kenta Tanaka, Yasushi Hashimoto, Yoshihiro Kobori, Yasushi Sato, Mahito Atobe
  • Organizer: PRiME 2020
  • Int'l Joint Research
• [Presentation] Electrocatalytic Asymmetric Hydrogenation of α,β-Unsaturated Acids in a PEM Reactor using Palladium-cinchona Catalysts (2020)
  • Author(s): Atsushi Fukazawa, Kenta Tanaka, Yasushi Hashimoto, Yoshihiro Kobori, Yasushi Sato, Mahito Atobe
  • Organizer: The 14th International Symposium on Organic Reactions
  • Int'l Joint Research
• [Presentation] Synthesis and Molecular Weight Control of Well-defined Polyphenylene using Electrochemical Polymerization in a Flow Microreactor (2020)
  • Author(s): Yuto Nakamura, Kenta Tanaka, Mahito Atobe
  • Organizer: The 14th International Symposium on Organic Reactions
  • Int'l Joint Research
• [Book] 有機電解合成の新潮流 (2021)
  • Author(s): 淵上寿雄、跡部真人、稲木信介
  • Total Pages: 340
  • Publisher: シーエムシー出版
  • ISBN: 9784781316260
• [Remarks] 跡部研究室ホームページ
  • URL: http://www.atobe-lab.ynu.ac.jp
• [Remarks] 跡部研究室ホームページ
  • URL: https://atobelabynu.wixsite.com/atobelab
• [Patent(Industrial Property Rights)] 環状アミンの製造装置及び環状アミンの製造方法 (2022)
  • Inventor(s): 跡部真人、信田尚毅、清水勇吾
  • Industrial Property Rights Holder: 跡部真人、信田尚毅、清水勇吾
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2022-134327
  • Filing Date: 2022