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Study on the Simultaneous Enantioseparation of Racemic Acid and Amine Combinations

Research Project

Project/Area Number 13555245
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 有機工業化学
Research InstitutionThe University of Tokyo

Principal Investigator

SAIGO Kazuhiko  The University of Tokyo, Graduate School of Frontier Sciences, Professor, 大学院・新領域創成科学研究科, 教授 (80016154)

Co-Investigator(Kenkyū-buntansha) KINBARA Kazushi  The University of Tokyo, Graduate School of Engineering, Lecturer, 大学院・工学系研究科, 講師 (30282578)
KOBAYASHI Yuka  The University of Tokyo, Graduate School of Engineering, Research Associate, 大学院・工学系研究科, 助手 (80334316)
SAKAI Kenichi  Yamakawa Chemical Industry Co., Ltd, Researcher, 研究開発部長(研究職)
酒井 建一  山川薬品工業株式会社, 研究開発部長(研究職)
Project Period (FY) 2001 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥13,400,000 (Direct Cost: ¥13,400,000)
Fiscal Year 2004: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 2003: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 2002: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2001: ¥4,700,000 (Direct Cost: ¥4,700,000)
KeywordsRacemic acid・racemic amine / Diastereomeric salt method / Conglomerate / Racemic compound / X-ray crystallographic analysis / CH-π相互作用 / キラル識別機構
Research Abstract

We have recently reported that the probability for conglomerate formation is as high as 50% in the crystallizations of racemic acid and amine combinations, for which efficient enantioseparation is achieved by the diastereomeric salt method. In order to confirm the generality of the phenomenon, we tried to extend the crystallization to various kinds of racemic acid and amine combinations. However, only a few racemic and enantiopure forms of acids and amines, which have been resolved with high efficiency, were found, despite of heavy bibliographic search. Therefore, novel resolving agents suitable for the present study were developed prior to the examination. Six kinds of novel acidic resolving agents, which have a naphthalene and/or phosphonothioic skeleton, and four kinds of novel basic resolving agents, which have a benzindanylene and/or bishydroxy skeleton, were designed and synthesized for the present study.
Using various kinds of resolving agents, which were reported in literatures and developed in the present study, crystallizations of racemic acid and amine combinations were carried out in order to analyze the probability of the formation of conglomerate. As a result, we found that the probability was also about 50% for a wide variety of the combination, as we have reported. Furthermore, it was clarified that the determination of conglomerate could be carried out not only by X-ray crystallographic analysis but also by IR spectral and melting point analyzes of a single crystal and powdery micro crystals, which were obtained in the crystallization of a racemic acid and amine combination.

Report

(5 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (18 results)

All 2005 2004 2003 Other

All Journal Article (12 results) Book (1 results) Publications (5 results)

  • [Journal Article] Synthesis, Absolute Configuration, and Application of Enantiopure trans-1-Aminobenz[f]indan-2-ol.2005

    • Author(s)
      Kobayashi Y, Kinbara K, Sato M, Saigo K.
    • Journal Title

      Chirality (17)2

      Pages: 108-112

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Synthesis, Absolute Configuration, and Application of Enantiopure trans-1-Aminobenz[f]indan-2-o12005

    • Author(s)
      Kobayashi, Y., Kinbara, K., Sato, M., Saigo, K.
    • Journal Title

      Chirality 17

      Pages: 108-112

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Rational Design of CH/π Interaction Sites in a Basic Resolving Agent.2004

    • Author(s)
      Kobayashi Y, Kurasawa T, Kinbara K, Saigo K.
    • Journal Title

      J.Org.Chem. 69

      Pages: 7436-7441

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] A new hydrogen-bonding motif for chiral recognition in the diastereomeric salts of racemic 1-phenylethylamine derivatives with enantiopure O-ethyl phenylphosphonothioic acid2004

    • Author(s)
      Kobayashi Y, Morisawa F, Saigo K.
    • Journal Title

      Org.Lett. 6(23)

      Pages: 4227-4230

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Supramolecular architecture consisting of an enantiopure amine and an achiral carboxylic acid : An application to the enantioseparation of racemic alcohols.2004

    • Author(s)
      Kobayashi Y, Kodama K, Saigo K.
    • Journal Title

      Org.Lett. 6(17)

      Pages: 2941-2944

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Rational Design of CH/π Interaction Sites in a Basic Resolving Agent2004

    • Author(s)
      Kobayashi, Y., Kurasawa, T., Kinbara, K., Saigo, K.
    • Journal Title

      J.Org.Chem. 69

      Pages: 7436-7441

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new hydrogen-bonding motif for chiral recognition in the diastereomeric salts of racemic 1-phenylethylamine derivatives with enantiopure O-ethyl phenylphosphonothioic acid2004

    • Author(s)
      Kobayashi, Y., Morisawa, F., Saigo, K.
    • Journal Title

      Org.Lett. 6

      Pages: 4227-4230

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Supramolecular architecture consisting of an enantiopure amine and an achiral carboxylic acid : An application to the enantioseparation of racemic alcohols2004

    • Author(s)
      Kobayashi, Y., Kodama, K., Saigo, K.
    • Journal Title

      Org.Lett. 6

      Pages: 2941-2944

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Resolution of 3-(methylamino)-1-(2-thienyl)propan-1-ol, a new key intermediate for duloxetine, with (S)-mandelic acid2003

    • Author(s)
      Sakai K, Sakurai R, Yuzawa A, Kobayashi Y, Saigo, K.
    • Journal Title

      Tetrahedron Asymm. 14

      Pages: 1631-1636

    • NAID

      120000872800

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Chiral discrimination of 2-arylalkanoic acids by (1S,2S)-1-aminoindan-2-ol and (1S,2S)-2-aminoindan-1-ol : Correlation of the relative configuration of the amino and hydroxy groups with the pattern of a supramolecular hydrogen-bond network in the less-soluble diastereomeric salt.2003

    • Author(s)
      Kinbara K, Katsumata K, Saigo K.
    • Journal Title

      Chirality 6

      Pages: 564-570

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Resolution of 3-(methylamino)-1-(2-thienyl)propan-1-o1, a new key intermediate for duloxetine, with (S)-mandelic acid2003

    • Author(s)
      Sakai, K., Sakurai, R., Yuzawa, A., Kobayashi, Y., Saigo, K.
    • Journal Title

      Tetahedron Asymm. 14

      Pages: 1631-1636

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Chiral discrimination of 2-arylalkanoic acids by (1S,2S)-1-aminoindan-2-o1 and (1S,2S)-2-aminoindan-1-o1 : Correlation of the relative configuration of the amino and hydroxy groups with the pattern of a supramolecular hydrogen-bond network in the less-soluble diastereomeric salt2003

    • Author(s)
      Kinbara, K., Katsumata, Y, Saigo, K.
    • Journal Title

      Chirality 6

      Pages: 564-570

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] Topics in Stereochemistry,23,(Ed. : S.C.Demark)2003

    • Author(s)
      Kinbara K., Saigo K.
    • Publisher
      Wiley & Sons : New York
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] K.Kimbara, Y.Katsumata, K.Saigo: "Chiral Discrimination of 2-Arylalkanoic Acids by (1S,2S)-1-Aminoindan-2-ol and (1S,2S)-2-Aminoindan-1-ol"Chirality. 15. 564-570 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kinbara, Y Katsumata, K.Saigo: "Chiral Discrimination of 2-Arylalkanoic Acids by (1S,2S)-1-Aminoindan-2-ol and (1S,2S)-2-Aminoindan-1-ol : Correlation of the Geometry of Amino and Hydroxy Group with the Pattern of the Supramolecular Hydrogen-Bond Network in the Less-Soluble Diastereomeric Salt"Chirality. (In press). (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Kinbara, Y Katsumata, K.Saigo: "Enantiopure trans-and cis-3-aminoindan-1-ols : preparation and application as novel basic resolving agents"Chemistry Letters. 3. 266-267 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Saigo, K.Kinbara, Y Katsumata: "3-Amino-1-indanol, method for synthesizing it from b -phenyl-b -alanine, and its use as resolving agent for optical resolution"PCT Int. Appl.. 21 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Kinbara, Y.Tagawa, K.Saigo: "Probability of spontaneously resolvable conglomerates for racemic acid/racemic amine salts predicted on the basis of the resu1ts of diastereomeric resolutions"TETRAHEDRON : ASYMMETRY. 12. 2927-2930 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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