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Studies on generalization of a new enantiomeric resolution phenomenon (Preferential Enrichment)

Research Project

Project/Area Number 10440187
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

TAMURA Rui  Kyoto University, Graduate School of Human and Environmental Studies, Professor, 大学院・人間・環境学研究科, 教授 (60207256)

Co-Investigator(Kenkyū-buntansha) HAYASHI Naoto  Kyoto University, Graduate School of Human and Environmental Studies, Assistant Professor, 大学院・人間・環境学研究科, 助手 (90281104)
Project Period (FY) 1998 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥7,600,000 (Direct Cost: ¥7,600,000)
Fiscal Year 2001: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2000: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1999: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1998: ¥4,000,000 (Direct Cost: ¥4,000,000)
KeywordsEnantiomeric Resolution / Preferential Enrichment / Racemic Mixed Crystal / Polymorphic Transition / Phase Transition / Crystal Structure / X-ray Crystallagraphy / Enantiomer / ラセミ混晶 / ラセミ結晶 / 結晶多形 / 多形転移 / 混晶 / ラセミ化合物 / 再結晶
Research Abstract

In order to elucidate the mechanism of Preferential Enrichment, the following four points must be fully understood; (i) the supramolecular association structure in solution, (ii) the crystal structure of the metastable crystalline phase formed kinetically from the supersaturated solution, (iii) the mechanism of polymorphic transition of the metastable crystalline phase into the stable form in the supersaturated solution. For the understanding of (i), the solubility and supersolubility measurement of the solid material, the number-averaged molecular weight measurement in solution, and the molecular dynamics simulation of the stable supramolecular association structure were carried out. For the isolation of the metastable crystals in (ii), the epitaxial crystallization by using seed crystals, or the selective crystallization of the desired polymorph by inhibition of the nucleation or crystal growth process of an undesired stable polymorph were used. In addition, when the single crystal f … More or X-ray crystallographic analysis was not available, the crystal structure was able to be solved from the powder X-ray diffraction data by the Monte Carlo method and the subsequent Rietveld refinement. For the aim of (iii), the in situ and real time AIR-IR measurement of the supersaturated solution or the DSC measurement of the deposited crystals was effective. It was also shown that the mechanism of polymorphic transition could be rationalized by comparison of the metastable and stable crystal structures. By using these methods, the following four results concerning the mechanism of Preferential Enrichment were obtained.
(1) In a solution of the racemate showing Preferential Enrichment, the homochiral molecular association is preferred to the heterochial one.
(2) The nature of the racemic crystal of the compound showing Preferential Enrichment has been classified as a fairly ordered racemic mixed crystal composed of the two enantiomers.
(3) The mechanism of Preferential Enrichment is closely associated with the polymorphic transition occurring during crystallization from the supersaturated solution.
(4) By comparison of the crystal structures before and after the phase transition, the mechanism of the solid-to-solid type of polymorphic transition can be understood. On the basis of this mechanism, the unique mechanism of Preferential Enrichment has been proposed. Less

Report

(5 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] R.Tamura: "Unusual disordered Crystal structure of the Racemate Exhibiting Novel Enantiomeric Resolution Phenomenon : Preferential Enrichment"Angewandte Chemie International Edition. 37. 2876-2878 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R.Tamura: "Comparison of Crystal Structures of New Racemic Chiral Compounds Showing and Not Showing the Phenomenon of Preferential Enrichment"Supramolecular Chemistry. 13. 71-78 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 田村類: "優先富化現象-結晶構造と多形転移-"日本化学会誌. 71-82 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H.Takahashi: "Preferential Enrichment : An Essential Crystal Structure"Enantiomer. 6. 57-66 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H.Takahashi: "Preferential Enrichment : Full Crystallographic Analysis of the Unusual Phenomenon in the Mixed Crystal's Version"Chirality. 14. 541-547 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R.Tamura: "Mechanism of Preferential Enrichment, an Unusual Enanriomeric Resolution Phenomenon Caused by Polymorphic Transition during Crystallization of Mixed Crystal Compossed of Two Enantiomers"Journal of The American Chemical Society. 124. 13139-13153 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R. Tamura: "Unusual Disordered Crystal Structure of the Racemate Exhibiting Novel Enantiomeric Resolution Phenomenon:Preferential Enrichment"Angewandte Chemie International Edition. Vol.37. 2876-2878 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R. Tamura: "Comparison of Crystal Structures of New Racemic Chiral Compounds Showing and Not Showing the Phinomenon of Preferential Enrichment"Supramolecular Chemishy. Vol.13. 71-78 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R. Tamura: "Preferential Enrichment: Crystal Shcture and Polymorphic Transition"Jopuranl of the Chemical Society of Japan, Chemistry and Industry. 71-82 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H. Takahashi: "Preferential Enrichment An Essential Crystal Structure"Enantiomer. Vol.6. 57-66 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H. Takahashi: "Preferental Enrichment: Full Crystallogmphic Analysis of the Unusual Phenomenon in ffie Mixed Crystal's Version"Chirality. Vol.14. 541-54v (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R. Tamura: "Mechanism of Preferential Enrichment, an Unusual Enantiomeric Resolution Phenomenon Caused by Polymorphic Transition during Crystallization of Mixed Crystals Composed of Two Enantiomers"Journal of the American Chemical Society. Vol.124. 13139-13153 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R.Tamura: "Comparison of Crystal Structures of New Racemic Chiral Compounds Showing and Not Showing the Phenomenon of Preferential"Supramolecular Chemistry. 13巻. 71-78 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.Takahashi: "Preferential Enrichment : An Essential Crystal Structure"Enamtiomer. 6巻. 57-66 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.Takahashi: "Preferential Enrichment : Full Crystallographic Analysis of the Unusual Phenomenon in the Mixed Crystals Version"Chirality. 14巻(印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 田村類: "優先富化現象-結晶構造と多形転移-"日本化学会誌. 2号. 71-82 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Tamura: "Preferential Enrichment and Crystal Structure"Molecular Crystal Liquid Crystal. 356巻. 185-194 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 田村類: "新しい光学分割現象:優先富化"日本結晶学会誌. 43巻1号. 32-37 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Tamura: "Comparison of Crystal Structures of New Racemic Chiral Compounds Showing and Not Showing Preferential Enrichment"Supramolecular Chemistry. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Takahashi: "Preferential Enrichment : An Essential Crystal Structure"Enantiomer. (印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Tamura: "Preferntial Enrichment and Crystal Structure"Molecular Crystal Liquid Crystal. 印刷中. (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] 田村 類: "光学分割の常識が変わる"化学. 54巻6号. 47-54 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] R.Tamura: "Unusual Disordered Crystal Structure of a Racemate Exhibiting a Novel Enantiomeric Resolution:Preforential Enrichment" Angewandte Chemie Internal Edition. 37巻20号. 2876-2878 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Tamura: "Ideal Enantiomeric Resolution (Preferential Enrichment) by Recrystallization of a Racemic Compound (Part 6)" Enantiomer. 3巻2号. 149-157 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 田村 類: "ラセミ結晶の新しい光学分割現象(優先富化)" 有機合成化学協会誌. 56巻1号. 22-33 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Takahashi: "Ideal Enantiomeric Resolution (Preferential Enrichment) by Recrystallization of a Racemic Compound (Part 5)" Chirality. 10巻7号. 705-710 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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