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Development of Photocatalytic Organic Synthesis Processes of Next Generation

Research Project

Project/Area Number 07555574
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section試験
Research Field 工業物理化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

NISHIMOTO Sei-ichi  Kyoto Univ., Grad.School Eng., Pro., 大学院・工学研究科, 教授 (10115909)

Co-Investigator(Kenkyū-buntansha) OHTANI Bunsho  Hokkaido Univ., Grad.School Sci., Assoc.Pro., 大学院・理学研究科, 助教授 (80176924)
井澤 邦輔  味の素(株), 中央研究所プロセス開発研究所・ファインケミカル開発室, 室長
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1996: ¥500,000 (Direct Cost: ¥500,000)
KeywordsPhotocatalyst / Amino Acid / Industrial Process / L-Lysine / L-Pipecolinic Acid / Reactor / Work-up Procedure / Ion-Exchange Resin / 医薬品原料 / ピペコリン酸 / 白金担持酸化チタン / 光学純度 / カルバミル化 / ε-アミノ基
Research Abstract

L-Pipecolinic acid, a kind of optically active cyclic imino acid, is a basic skeleton of piperidine alkaloids and useful intermediate for the organic synthesis of various drugs. However, at present, there have not been industrial synthesis procedures. This project aims to develop a novel method to obtain optically active L-pipecolinic acid from L-lysine, which is a cheap starting material produced via an industrial fermentation process. First, screening of photocatalyst was achieved and found that a commercially available titanium (IV) dioxide (titania) as well as newly developed laboratory-made titanias (via HyCOM,TD,and THyCA procedures) showed markedly high photocatalytic activity to produce L-pipecolinic acid readily and selectively. The role of platinum particles loaded on, with various methods, titania has been also clarified ; sufficient loading of dispersed platinum particles is requisite for the best photocatalyst. Such properties of platinum-loaded titanias were alSo investigated with the photocatalytic transfer hydrogenation of Schiff bases. During this screening, it was also clarified that amorphous, but not titanium (IV) hydroxide nortitania hydrate, is completely inactive toward photocatalytic reactions maybe due to the higher possibility of recombination of photoexcited electron and positive hole. Second, the mechanism of the photocatalytic N-cyclization of L-lysine was investigated by usig platunm-looded titanias. It is observed that the positive holes oxidize amino group in L-lysine intoimine which is then hydrolyzed to carbonyl compounds and intramolecularly condensed with remaining amino group into cyclic schiff base intermediate. This is reduced by photoexcited electrons to give final product, L-pipecolinic acid.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (17 results)

All Other

All Publications (17 results)

  • [Publications] B.Ohtani: "Photocatalytic Transfer Hydrogenation of Schiff Bases with Propan-2- of by Suspended Semiconductor Partloles Loaded with Platinum Deposits" J.Chem.Soc.,Faraday Trans.92. 4291-4295 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Kominami: "Photocatalytic Minaralization of Aoetic Acid in Asrated Aquaoua Suspenalone of Ultra-highly Active Titanium (IV) Oxide Prepared by Hydrothermal Cryatallization in Toluene" Chem.Lett.1051-1052 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] B.Ohtani: "Aninsltu FT-IR Study on Photocatalytic Reaction at Semiconduct or -Aqueous Solution Interface‥Mechanism of Photooatalytio N-Cyclization of L-Lysine" Chem.Lett.91-92 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] B.Ohtani: "Role of Platinum Deposits on Titanium (IV) Oxide Particies : Structural and Kinatic Analyses of Photocatalytio Reaction in Aqueous Alcohl and Amino Solutions" J.Phys.Chem.101(印刷中). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] B.Ohtani: "Photooatalytic Activity of Amorphous-Anatase Mixture of Titanium (IV) Oxide Particles Suspended in Aqueous Solutions" J.Phys.Chem.101(印刷中). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Kominami: "Novel Synthesis of Miaroaryat alline Titanium (IV) Oxide Having High Thermal Stability and Ultra-High Photooat Alytic Activity : Thermal Decomposition of Titanium (IV) Alkoxide in Organic Solvents" Catal.Lett.(印刷中). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ohtani, Bunsho ; Goto, Yosuke ; Nishimoto, Sei-ichi ; Inui, Tomoyuki: "Photocatalytic Transfer Hydrogenation of Schiff Bases with Propan-2-ol by Suspended Semiconductor Particles Loaded with Platinum Deposits" J.Chem.Soc., Faraday Trans.92. 4291-4295 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Kominami, Hiroshi ; Kato, Jun-ichi ; Kohno, Masaaki ; Kera, Yoshiya ; Ohtani, Bunsho: "Photocatalytic Mineralization of Acetic Acid in Aerated Aqueous Suspensions of Ultra-highly Active Titanium (IV) Oxide Prepared by Hydrothermal Crystallization in Toluene" Chem.Lett.1051-1052 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ohtani, Bunsho ; Yako, Takayuki ; Samukawa, Yoriaki ; Nishimoto, Sei-ichi ; Kanamura, Kiyoshi: "An in situ FT-IR Study on Photocatalytic Reaction at Semiconductor-Aqueous Solution Interface--Mechanism of Photocatalytic N-Cyclization of L-Lysine" Chem.Lett.91-92 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ohtani, Bunsho ; Iwai, Kunihiro ; Nishimoto, Sei-ichi ; Sato, Shinri: "Role of Platinum Deposits on Titanium (IV) Oxide Particles : Structural Analyzes and Kinetic Simulation of Photocatalytic Reaction in Aqueous Alcohol and Amino Acid Solutions" J.Phys.Chem.(in press.). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ohtani, Bunsho ; Ogawa, Yoshimasa ; Nishimoto, Sei-ichi: "Photocatalytic Activity of Amorphous-Anatase Mixture of Titanium (IV) Oxide Particles Suspended in Aqueous Solutions" J.Phys.Chem.(in press.). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Kominami, Hiroshi ; Kato, Jun-ichi ; Takada, Yoko ; Doushi, Yoshiaki ; Ohtani, Bunsho ; Nishimoto, Sei-ichi ; Inoue, Masashi ; Inui, Tomoyuki ; Kera, Yoshiya: "Novel Synthesis of Microcrystalline Titanium (IV) Oxide Having High Thermal Stability and Ultra-High Photocatalytic Activity : Thermal Decomposition of Titanium (IV) Alkoxide in Organic Solvents" Catal.Lett.(in press). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] B.Ohtani: "Photocatalytic Transfer Hydrogenation of Schiff Bases with Propan-2-ol by Suspended Semiconductor Particles Loaded with Platinum Deposits" J.Chem.Soc.,Faraday Trans.92. 4291-4295 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Kominami: "Photocatalytic Mlnerallzation of Acetlc Acid in Aerated Aqueous Suspensions of Ultra-highly Active Tltanlum (IV) Oxide Prepared by Hydrothermal Crystallization in Toluene" Chem.Lett.1051-1052 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] B.Ohtani: "Aninsitu FT-IR Study on Photocatalytic Reaction at Semiconductor-Aqueous Solution interface--Mechanism of Photocatalytic N-Cycllzation of L-Lysine" Chem.Lett.91-92 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] B. Ohtani: "Effect of Platinum Loading on the Photocatalytic Activity of Cadmium(II)Sulfide Particles Suspended in Aqueous Amino Acid Solutions" J. Photochem. Photobiol., A: Chem.90. 75-80 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] B. Ohtani: "Photocatalytic Racemization of Amino Acids in Aqueous Polycrystal-line Cadmium(II)Sulfide Dispersions" J. Chem. Soc., Faraday Trans.91. 1103-1109 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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