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Design of Reactions in Crystals

Research Project

Project/Area Number 06242104
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionEhime University

Principal Investigator

TODA Fumio  愛媛大学, 工学部, 教授 (50036232)

Co-Investigator(Kenkyū-buntansha) TANAKA Koichi  愛媛大学, 工学部, 助教授 (10116949)
OHASHI Yuji  東京工業大学, 理学部, 教授 (40016118)
KAI Yasushi  大阪大学, 工学部, 教授 (40029236)
OKAMOTO Yoshio  名古屋大学, 工学部, 教授 (60029501)
Project Period (FY) 1994 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥36,100,000 (Direct Cost: ¥36,100,000)
Fiscal Year 1997: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1996: ¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 1995: ¥12,300,000 (Direct Cost: ¥12,300,000)
Fiscal Year 1994: ¥10,800,000 (Direct Cost: ¥10,800,000)
Keywordsorganic solid state chemistry / solid state reaction / enantioselective reaction / crystal chemistry / molecular movement in crystal / solid state photoreaction / 固体表面 / 有機固体化学 / 不斉選択的反応 / 結晶化学 / 結晶中の分子移動 / 固体光反応 / 公開シンポジウム / 班会議 / ニュースレター / 班員間の連絡 / 総括班会議 / 国際研究集会 / パネル討論会 / 固相有機化学反応 / 不斉認識 / 国際会議 / 特別シンポジウム / 評価班 / 講演要旨集 / 研究業績集
Research Abstract

平成6年度に始まり平成8年度に終了した重点領域研究「有機結晶環境下での反応設計」の取りまとめを行った。この3年間の研究で得られた研究成果は著しく、研究論文は800編余りになり、口答発表は数千件にもなる、総説や図書も数多いし、国内外での招待講演数も多い。得られた研究業績の主だったものの概要は次の通りである。有機結晶中や結晶間で光反応や熱反応が起こるとを見出して、数多くの無溶媒有機合成反応を確立した。これらの固体反応はX線結晶構造解析や熱測定及び現論計算によって詳細に検討された。
更に、結晶中の熱反応は固体表面だけで無く、結晶の中でも比較的容易に起こる極めて興味深い発見がもたらされた。例えば、結晶全体に空気中の酸素が浸透して、結晶が破壊されることなく酸化反応が定量的に起こることが見出だされた。又、結晶を加熱すると、トランス体の大きな置換基が転移してシス体に変換したのち熱環化反応を起こす反応が、結晶が破壊されること無く進行し得ると言う極めて重大な発見があった。これまで、シクロデキストリンの穴に高分子物質が溶液中で接触するとシクロデキストリンの穴に高分子が入り込むことが知られていたが、この現象は固相即ち無溶媒下でも起こることが見出だされ、固相で分子移動が容易に起こることが再確認され、これからの化学に新しい領域を開拓する重要なヒントを与えた。

Report

(5 results)
  • 1997 Annual Research Report
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (54 results)

All Other

All Publications (54 results)

  • [Publications] T.Asahi, M.Nakamura, J.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´-dihydroxy-1,1´-binaphthyl by Conplexation" J.Chem.Soc., Chem.Commun.1087-1088 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda, K.Kanemoto: "Solvent Free Synthetic Procedure Throughoat Reaction and Separation:Ylide Reaction with Alkyl Aryl Ketones in the Absence of Solvent" Heterocycles. 46. 185-188 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] E.Yashima, M.Yamada, C.Yamamoto, M.Nakashima, Y.Okamoto: "Chromato graphic Enantioseparation and Chiral Discrimination in NMR by Trisphenylcarbamates Derivatives of Cellulose, Oligosaccharides, and Cyclodextrins" Enantiomer. 2. 225-240 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] E.Yashima, P.Sahavattanapong, C.Yamamoto, Y.Okamoto: "Chiral Discrimination by 4-Chloro-and 4-Bromophenylcarbamates of Moltooligosa ccharides in HPLC, NMR and CD." Bull. chem. Soc. Jpn. 70. 1977-1984 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Yamamoto, T.Ueda, N.Kanehisa, K.Miyawaki, Y.Takai, S.Tagawa, M.Sawada, Y.Kai: "Selective Dimerization by a Radical Chain Reaction in γ-irradiated Crystals of 1,3-Bis (3-acetoxyprop-1-ynyl) -4-methoxy-b-methylbenzene" J. Chem. Soc., Perkin Trans. 2. 743-747 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Ueda, T.Sugimoto, T.Tada, N.Kanehisa, Y.Kai: "Temperatine Dependence of Crystal Structures, and Electrical Conducting and Magnetic Properies in Plate Crystals of 1:2 Tetrafluorotetracyanozuinodimethane" Mol. Cryst. Liq. Cryst.296. 323-333 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Ohgo, Y.Ohashi, W.T.Klooster T.F.Koetzle: "Analysis of Hydrogen-Deuiterium Exchange Recoction in a Crystal by Neutron Ditlaction" Enantiomer. 2. 241-248 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Sekine, H.Tatsuki, Y.Ohashi: "Crystalline-state β-α Photoisomerization of Cobaloxince Complexes, Part 1. Generation of Asymmetry in Chiral Crystal Environment" J. Organomet. Chem.536. 389-398 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Koura, Y.Ohashi: "β-α Photoisomerization of Cobaloxime Complexes in the Solid State. 6. Asymnetric lnduction Due to Chiral Crystal Environment" Bull. Chem. Soc. Jpn. 70. 2417-2423 (1997)

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

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

    • Related Report
      1997 Annual Research Report
  • [Publications] 岡本佳男, 八島栄次: "最新の分離・精製・検出法-原理から応用まで-「光学活性医薬品の分析」" エヌ・ティー・エス, 668-680 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] E,Yashima, Y,Okamoto: "The lmpact of Stereochemistry on Drug Development and Use ゙Chiral Recoqnition Mechanism of Polysaecharides Chiral Stationary Phase" John Wiley, 345-376 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] F.Toda,H.Liu,I.Miyahara and K.Hirotsu: "Design of new host compounds,1,1-bis(diarylhydroxymethyl)ferrocenes" J.Chem.Soc.,Perkin Trans.2. 85-88 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda,H.Miyamoto,S.Kikuchi,R.Kuroda and F.Nagami: "Enantioselective Photocyclization of 2-Arythio-3-methylcyclohexen-1-ones to Dihydro-benzothiophene Derivatives in an Inclusion Crystal with an Optically Active Host" J.Am.Chem.Soc.118. 11315-11316 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] G.Kaupp,J.Schmeyers,F.Toda,H.Takumi and H.Koshima: "Mechanism of Solid-Solid Resolution of Pantolactone" J.Phys.Org.Chem.9. 795-800 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.R.Caira,A.Coetzee,L.R.Nassimbeni and F.Toda: "Inclusion of Dioxolane by a Tricyclic Diol Host:Structure and Kinetics" J.Chem.Research(s). 280-281 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda,H.Takumi and K.Tanaka: "A Simple Preparative Method for Optically Active Glycidic Esters" Tetrahedron:Asymmetry. 6・5. 1059-1062 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda and N.Imai: "Ylide Reaction in the Solid State:a simple procedure for the Synthesis of Cyclopropanes,Oxiranes and Aziridines" J.Chem.Soc.,Perkin Trans.1. 2673-2674 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Fumio Toda: "Comprehensive Supramolecular Chemistry:Volume 6,Solid-State Supramolecular Chemistry:Crystal Engineering,"Diol,Bisphenol,and Diamide Host Compounds"" Pergamon, 966 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Tanaka and F.Toda: "Comprehensive Supramolecular Chemistry:Volume 6,Solid-State Supramolecular Chemistry:Crystal Engineering,"Onium Salt Hosts"" Pergamon, 966 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda, H.Liu, I.Miyahara and K.Hirotsu: "Design of new host compounds, 1,1-bis (diarylhydroxymethyl) ferrocenes" J.Chem.Soc., Perkin Trans.2. 85-88 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda, H.Miyamoto, S.Kikuchi, R.Kuroda and F.Nagami: "Enantioselective Photocyclization of 2-Arylthio-3-methylcyclohexen-1-ones to Dihydrobenzothiophene Derivatives in an Inclusion Crystal with an Optically Active Host" J.Am.Chem.Soc.118. 11315-11316 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] G.Kaupp, J.Schmeyers, F.Toda, H.Takumi and H.Koshima: "Mechanism of Solid-Solid Resolution of Pantolactone" J.Phys.Org.Chem.9. 795-800 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.R.Caira, A.Coetzee, L.R.Nassimbeni and F.Toda: "Inclusion of Dioxolane by a Tricyclic Diol Host : Structure and Kinetics" J.Chem.Research (s). 280-281 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda, H.Takumi and K.Tanaka: "A Simple Preparative Method for Optically Active Glycidic Esters" Tetrahedron : Asymmetry. 6 (5). 1059-1062 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda and N.Imai: "Ylide Reaction in the Solid State : a simple procedure for the Synthesis of Cyclopropanes, Oxiranes and Aziridines" J.Chem.Soc., Perkin Trans.1. 2673-2674 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Fimio Toda: Diol, Bisphenol, and Diamide Host Compounds in "Comprehensive Supramolecular Chemistry : Volume 6, Solid-State Supramolecular Chemistry : Crystal Engineering". Pergamon, 465-516 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Tanaka and F.Toda: Onium Salt Hosts in "Comprehensive Supramolecular Chemistry : Volume 6, Solid-State Supramolecular Chemistry : Crystal Engineering". Pergamon, 517-534 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] F.Toda,H.Liu,I.Miyahara and K.Hirotsu: "Design of new host compounds,1,1-bis (diatyhydroxymethl) ferrocenes" J.Chem.Soc.Perkin Trans.2. 85-88 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] F.Toda,H.Miyamoto,S.Kikuchi,R.Kuroda and F.Nagami: "Enantioselective Photocyclization of 2-Arylthio-3-methylcyclohexen-1-onesto Dihydrobenzothiophene Derivatives in an Inclusion Crystal with an Optically Active Host" J.Am.Chem.Soc.118. 11315-11316 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] G.Kaupp,J.Schmeyers,F.Toda,H.Takumi and H.Koshima: "Mechanism of Solid-Solid Resolution of Pantolactone" J.Phys.Org.Chem.9. 795-800 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.R.Caira,A.Coetzee,L.R.Nassimbeni and F.Toda: "Inclusion of Dioxolane by a Tricyclic Diol Host : Structure and Kinetics" J.Chem.Research (s). 280-281 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] F.Toda and M.Ochi: "Enantioselective Oxidation of Imines in Inclusion Complex with a Chiral Host Compound and Preparation of Optically Pure Oxaziridines by Enantiomer Resolution" Enantiomer. 1. 85-88 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.A.Bourne,K.L.Gifford Nash and F.Toda: "Inclusion compounds with a sexipedal host. Crystal structures and thermal analysis of inclusion compounds of hexakis (3-hydroxy-3,3-diphenylprop-2-ynyl) benzene with methyl ethyl ketone,diethyl ketone and diethyl ether" J.Chem.Soc.,Perkin Trains.2. 2145-2149 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Fumino Toda: "Comprehensive Supramolecular Chemistry : Volume6,Solid-State Supramolecular Chemistry : Crystal Engineering,"Diol,Bisphenol,and Diamide Host Compounds"" Pergamon, 966 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Tanaka and F.Toda: "Comprehensive Supramolecular Chemistry : Volume6,Solid-State Supramolecular Chemistry : Crystal Engineering,"Onium Salt Hosts"" Pergamon, 966 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 戸田 芙三夫: "A Simple Preparative Method for Optically Active Glycidic Esters" Tetrahedron Asymm.6. 1059-1062 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 戸田 芙三夫: "Achiral Molecules Move and Order Themselves in a Chiral Form in Host-Guest Inclusion Crystals" Chem.Lett.809-810 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 岡本 佳男: "Ply [4- (carboxyphenyl)] acetylene as a Probe for Chirality Assignment of Amines by Circular Dicroism" J.Am.Chem.Soc.117. 11596-11597 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 甲斐 泰: "Synthesis and Structures of Tricyclic Diureas" J.Org.Chem.60. 7058-7062 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大橋 裕二: "Potassium Salt of a Synthetic Carboxyxli Ionophore" Acta Cryst.C51. 1816-1819 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 田中 耕一: "Optical Resolution of Methyl Phenyl and Benzyl Methyl Sulfoxides and Alkyl Phenylsulfinates" J.Chem.Soc.,Chem.Commun.639-640 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 岡本 佳男: "化学便覧・応用編 II" 日本化学会, 5670 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 甲斐 泰: "The 24th Seminar on Science adn Technology" Kyowa Insatu, 335 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Fumio Toda et al: "Selective Inclusion Crystallization of Phenol Derivatives with Tetralkylammonium Salts" Supramol Chem.3. 291-298 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda et al: "Structures and Photoreactivities of N-Isopropyl-N-methylphenylglyoxylamide Included inClathrate" Bull.Chem.Soc.Jpn.67. 985-993 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda et al: "A New Synthetic Route to 1、1、6、6-Tetraalkylhexa-1、2、4、5-tetraene by Selective Reduction" J.Chem.Soc.Perkin Trans.1. 2043-2044 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda et al: "The Mechanism of the Enantioselective Photocyclization of 2-Piperidine in the Clathrate Crystal" Bull.Chem.Soc.Jpn. 67. 2383-2387 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda et al: "A New Simple Chiral Helicene,3、4-Bis(diphenyl-methylene)-N-methylsuccimide in Its Chiral Crystal" Supramol Chem.3. 87-88 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda et al: "Inclusion Compounds N、N、N'、N'-Tetracyclohexyl-fumaramide with Isomers of Cresol and Water" J.Chem.Crystal.24. 545-552 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda: "Reactivity in Molecular Crystals" Kodansha (Tokyo), 348 (1993)

    • Related Report
      1994 Annual Research Report
  • [Publications] Fumio Toda: "Advances in Strain in Organic Chemistry" JAI Press (London), 280 (1993)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2017-05-19  

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