• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Study on Dynamic Molecular Behaviors in Crystal

Research Project

Project/Area Number 09044091
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionOkayama University of Science (1999)
Ehime University (1997-1998)

Principal Investigator

TODA Fumio  Okayama University of Science, Department of Chemistry Professor, 理学部, 教授 (50036232)

Co-Investigator(Kenkyū-buntansha) MIYAMOTO Hisakazu  Ehime Univ., Applied Chemistry, Assistant Prof., 工学部, 助手 (30229893)
TANAKA Koich  Ehime Univ., Applied Chemistry, Associate Prof., 工学部, 助教授 (10116949)
TOYOTA Shinji  Okayama Univ. of Science, Chemistry, Associate Prof., 理学部, 助教授 (80207646)
KAUPP Gerd  オルテンプルグ大学, 化学部, 教授
BEROVA Nina  コロンビア大学, 化学部, 教授
小島 秀子  愛媛大学, 工学部, 助教授 (20304644)
SCHMEYERS Je  オルデンブルグ大学, 化学部, 助手
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥6,800,000 (Direct Cost: ¥6,800,000)
Fiscal Year 1999: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1998: ¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1997: ¥2,900,000 (Direct Cost: ¥2,900,000)
KeywordsDynamic Behaviors of Molecules in Crystal / Chemical Reactions in Crystal / Reaction from Single-Crystal-to-Single-Crystal / Enantioselective Reactions / Inclusion Complex Crystal / 包接錯体結晶 / 酒石酸ダイマーホスト / 光学分割 / X線構造解析 / 分子集合体 / 結晶 / AFM測定 / ホスト-ゲスト錯体 / 分子移動 / ジアレン / 熱環化反応 / 固体のCDスペクトル / 誘起CDスペクトル / ラセミ体結晶 / 不斉光反応
Research Abstract

When crystals of diallene derivative (A) is heated for 1h, dimethylencecyclobutene derivative (B) is produced by a cyclization reaction. Since A has a s-trans structure on crystal, isomenzation reaction from the s-trans configuration to a s-cis one should be occurred before the cyclization reaction. It is very interesting that such the big molecular motion occurs in a small space of crystal. It was also confirmed that the thermal conversion proceeds stereoselectively.
When a prochiral molecule is included in a chiral host compound, the former is arranged in a chiral form in its inclusion crystal and its inadiation gave optically active photoreaction product. In most cases of the photoreaction in crystal, crystalline lattice of the inclusion compound is destroyed as the reaction proceeds. On the contrary, photodimerzation of cyclohexenone, coumarin, and thiocoumarin in inclusion complex crystal with optically active host compound proceeded from single-crystal-to-single-crystal and enantioselectively to give corresponding optically active dimer. These reactions were studied by X-ray analysis.
Some other organic solid state reactions were also developed. For example, Dieckmann reaction, azomethine formation reaction, and Michael addition reaction were found to proceed efficiently in the solid state. Of these reactions, azomethine formation reaction was studied carefully by AFM method.
Solvent-free reactions were also clarified to proceed selectively. For example, treatment of stilibene and chalcone with pyridine-HBr-BrィイD22ィエD2 salt in the solid state gave meso- and erythro- addition product, respectively. These data clearly show that molecules in crystal move easily and that reaction occurs selectively and efficiently in the solid state.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (43 results)

All Other

All Publications (43 results)

  • [Publications] Fumio Toda: "Extremely Long C-C Bond in (-)-trans-1, 2-Di-tert-butyl-1, 2-diphenyl- and 1, 1-Di-tert-butyl-2, 2-diphenyl-3, 8-dichlorocyclobuta[b]naphthalenes"J. Org. Chem.. 64. 3102-3105 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "The crystal and molecular structure of 2, 7-di-tert-4, 5, 9, 10-tctraphenylbenzo[1, 2 : 4, 5]dicyclobutadiene"Chem. Commum.. 319-320 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Stereoselective Thermal Conversion of s-trans-Diallene Into Dimeyhylenecyclobutene via s-cis-Diallene in the Crystalline State"Angew. Chem. Int. Ed.. 37. 2724-2727 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Enantioselective Photochemical Reaction of N-Phenyl Enaminones in Inclusion Complex Crystals Using a Chiral Host Compound"J. Org. Chem.. 64. 2690-2693 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Effect of Overcrowding in [n]Radialenes on the Synthesis of Bis[4]radialenes"J. Org. Chem.. 64. 2287-2292 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "A New Host 2,3,6,7,10,11-Hexahydroxytriphenylene Which Forms Chiral Inclusion Crystalline Lattice : X-Ray Structural Study of the Chiral Crystalline Lattice"J. Phys. Org. Chem.. 12. 1-7 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Extremely Long C-C Bond in (-)-trans-1, 2-Di-tert-butyl-1, 2-diphenyl-and 1, 1-Di-tert -butyl-2, 2-diphenyl-3, 8-dichlorocyclobuta〔b〕naphthalenes"J. Org. Chem.. 64. 3102-3105 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "The crystal and molecular structure of 2, 7-di-tert-4, 5, 9, 10-tetraphenylbenzo〔1, 2 : 4, 5〕dicyclobutadiene"Chem. Commum.. 319-320 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Stereoselective Thermal Conversion of s-trans-Diallene into Dimeyhylenecyclobutene via s-cis-Diallene in the Crystalline State"Angew. Chem. Int. Ed.. 37. 2724-2727 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Enantioselective Photochemical Reaction of N-Phenyl Enaminones in Inclusion Complex Crystals Using a Chiral Host Compound"J. Org. Chem.. 64. 2690-2693 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Effect of Overcrowding in 〔n〕Radialenes on the Synthesis of Bis〔4〕radialenes"J. Org. Chem.. 64. 2287-2292 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "A New Host 2, 3, 6, 7, 10, 11-Hexahydroxytriphenylene Which Forms Chiral Inclusion Crystalline Lattice : X-Ray Structual Study of the Chiral Crystalline Lattice"J. Phys. Org. Chem.. 12. 1-7 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Fumio Toda: "Extremely Long C-C Bond in (-)-trans-1,2-Di-tert-butyl-1,2-diphenyl- and 1,1-Di-tert-butyl-2,2-diphenyl-3,8-dichlorocyclobuta[b]naphthalenes"J.Org.Chem. 64. 3102-3105 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Fumio Toda: "The crystal and molecular structure of 2,7-dei-tert-4,5,9,10-tetraphenylbenzo[1,2;4,5]dicyclobutadiene"Chem,Commum. 319-320 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Fumio Toda: "Stereoselective Thermal Conversion of s-trans-Diallene into Dimeyhylenecyclobutene via s-cis-Diallene in the Crystalline State"Angew.Chem.Int.Ed.. 37. 2724-2727 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] Fumio Toda: "Enantioselective Photochemical Reaction of N-phenyl Enaminones in Inclusion Complex Crystals Using a Chral Host Compound"J.Org.Chem.. 64. 2690-2693 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Fumio Toda: "Effect of Overcrowding in [n]Radialanes on the Synthesis of Bis[4]radialenes"J.Org.Chem.. 64. 2287-2292 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Fumio Toda: "A New Host 2,3,6,7,10,11-Hexahydroxytriphenylene Which Forms Chiral Inclusion Crystalline Lattice : X-Ray Stractural Study of the Chiral Crystalline Lattice"J.Phys.Org.Chem.. 12. 1-7 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] F.Toda,T.Suzuki,S.Higa: "Solvent-free Dieckmann Condensations of Diethyl Adipate and Pimerate" J.Chem.Soc.,Perkin Trans.1. 3521-3522 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,H.Koshima,S.I.Khan: "Isolation of Monomeric s-trans-Acrylic Acid as an Inclusion Crystal with Hydroxy Host Compound which Shows Anomalous C=O stretching Absorptions" J.Chem.Soc.Chem.Commun.2503-2504 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,T.Tamashima,M.Kato: "Steroselective Thermal Conversion of s-trans-Diallene to Dimethylenecyclobeutene via s-cis-Diallene in Crystalline State" Angew.Chem.Int.Ed.Engl.37. 2724-2727 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.K.Baldrodge,Y.Kasahara,K.Ogawa,J.S.Siegel,K.Tanaka,F.Toda: "The Nature of the Long Bond in 3,8-Dichloro-1,1,2,2-tetraphenylcyclobuta[b]naphthene" J.Am.Chem.Soc.120. 6167-6168 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] F.Toda,K.Tanaka,M.Kato: "Stereoselective Photodimerisation of Chalcones in the Molten State" J.Chem.Soc.Perkin Trans.1. 1315-1318 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] J.Schemyers,F.Toda,J.Boy,G.Kaupp: "Quantitative Solid-Solid Synthesis of Azomethines" J.Chem.Soc.,Perkin Trans.2. 989-993 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] F.Toda,H.Takumi,M.Nagami,K.Tanaka: "A Novel Method for Michael Addition and Epoxidation of Chalcones in A Water Suspension Medium: A Completely Organic Solvent-Free Synthetic Procedure" Heterocycles. 47. 469-479 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.R.Caira,A.Horne,L.R.Nassimbeni,F.Toda: "Inclution and Separation of Lutidine Isomers by a Diol Host Compound" Supramol.Chem.9. 231-237 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.R.Caira,A.Horne,L.R.Nassimbeni,F.Toda: "Selective inclusion of aliphatic alcohols by a diol host compound" J.Mater.Chem.8. 1481-1484 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Tamura,H.Takahashi,K.Hirotsu,Y.Nakajima,T.Ushio,F.Toda: "Unusual Disordered Crystal Structure of Racemate Exhibiting a Nobel Enantiomeric Resolution: Preferential Enrichement" Angew.Chem.Int.Ed.Engl.37. 2876-2878 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] R.Tamura,H.Takahashi,T.Ushio,Y.Nakajima,K.Hirotsu,F.Toda: "Ideal Enantiomeric Resolution(Preferential Enrichment)by Recrystallization of a Racemic Compound(Part 6): Hydrogen Bonding Mede in the Crystal Structure" Enantiomer. 3. 149-157 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.A.Bourne,K.L.Gifford Nash and F.Toda: "An Unnsual Mixed-guest Inclusion Compound. Crystal Structures of the Host Compound Hexakis(3-hyroxy-3,3,-diphenylprop-2-ynyl)benzene,and its Inclusion Compound with Acetonitrile and Benzene" J.Inclu.Phenom.Mol.Recog.Chem.32. 91-102 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] D.Hashizume,H.Koga,Y.Ohashi,H.Miyamoto,F.Toda: "Crystal Structure of N,N-Diisopropyl(3-methyl)phenylglyoxylamide" Analytical Sciences. 14. 1187-1188 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T, Asahin, M.Nakamara.S.Kobayashi, F.Toda.H.Miyamoto: "Optical Activity of Oxo Amide Crystals" J.Am.Chem,Soc.119. 3665-3669 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, K.Tanaka: "New Chiral Ammonium Salt Hosts Derived from Amino Acids : Very Efficient Optical Resolution of 2、2'=Dilvydioxy1,1'binaplittyl" J.Chem.Soc.,Chem.Commun. 1087-1088 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, K.Kanemoto: "Stvent Free Synthetic Procedure throughout Reaction and Separation:Yl;de Reaction with Alkyl Aryl Kotones" Heterocycles. 46. 185-188 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, H.Takumi, M.Nagami, K.Tanaka: "A Novel Method for Michael Addition and Epoxidation of Chalcones in a Water Suspension Medium" Heterocycles. 47. 469-479 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, K.Tanaka, R.Kuroda: "Isolation of a Nearly Eclipsed Chiral Rotamer of 1,2-Dichloro-ethane as an lnclusion Crystal with a chiral Host Compound" J.Chem,Soc.,chiem.Commun.1227-1228 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Tanaka, A.Moriyama, F.Toda: "Novel Chiral Recognition in Host-Guest lnclusion Complexes Depends on their Molar Ratios" J.Org,Chem.62. 1192-1193 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, K.Tanaka, H.Miyamoto, H.Koshima, I.Miyahara, K.Hiratsu: "Formation of Racemic Compound Crystals by Mixing Two Erautiomeric Crystals in the solid state" J.Chem,Soc.Perkin Trans.2. 1877-1885 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, H.Liu.I.Miyahara, K.Hirabtsu: "Design of New Host Compounds,1、1-Bis(diarylhydroxymetyl)terrocene" J.Chem.Soc.,Perkin Traus.2. 85-88 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] G.Kaupp, J.Boy: "Overlong C-C Single Bonds" Augew.Chem,lut.Ed-Engl.,. 36. 48-49 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Matile, N.Berova, K.Nakanishi, J.Fleischhauer: "Structural Studies by Exciton Coupled Circulai Pichroism over a Large Distance:Porphyrin Derivatives of Steroids, Dimeric Steroids" J.Am,Chiem.Soc. 118. 5198-5206 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Harada, N.Koumura, B.L.Feringa: "Chemistry of Unigue Chiral oletins.3,Synthesis and Absolute Stereochemistry of trans-and cis-1,1´,2,2´,3,3´,4,4´- biplenauthrylidenes" J.Am,Chiem.Soc.119. 7256-7264 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, H.Miyamoto, H.Koshima, Z.Lipkowska: "Chiral Arrangement of N-Ethyl-N-isopropylphenylglyoxylamide Molecule in its oun crystal and in an lnclusion Crystal with a Host Compound." J.Org.Chiem.62. 9261-9266 (1997)

    • Related Report
      1997 Annual Research Report

URL: 

Published: 1997-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi