1997 Fiscal Year Annual Research Report

有機結晶環境下での反応設計

Research Project

Project/Area Number	06242104
Research Institution	Ehime University
Principal Investigator	戸田芙三夫愛媛大学, 工学部, 教授 (50036232)
Co-Investigator(Kenkyū-buntansha)	田中耕一愛媛大学, 工学部, 助教授 (10116949) 大橋裕二東京工業大学, 理学部, 教授 (40016118) 甲斐泰大阪大学, 工学部, 教授 (40029236) 岡本佳男名古屋大学, 工学部, 教授 (60029501)
Keywords	研究業績 / 光反応 / 熱反応 / 無溶媒有機合成反応 / 固体反応 / X線結晶構造解析 / 固体表面
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。

Research Products
(14 results)

All Other

All Publications (14 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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)
[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)

1997 Fiscal Year Annual Research Report

有機結晶環境下での反応設計

Principal Investigator

戸田 芙三夫 愛媛大学, 工学部, 教授 (50036232)

Research Products

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

[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)

戸田芙三夫愛媛大学, 工学部, 教授 (50036232)