1991 年度実績報告書

特異な分子場の設計に基づく物質変換

研究課題

研究課題/領域番号	02303003
研究機関	東京大学
研究代表者	岡崎廉治東京大学, 理学部, 教授 (70011567)
研究分担者	富岡秀雄三重大学, 工学部, 教授 (20024599) 高谷秀正京都大学, 工学部, 教授 (40022644) 小林啓二東京大学, 教養学部, 教授 (50012456) 宇根山健治岡山大学, 工学部, 教授 (00033150) 青山安宏長岡技術科学大学, 工学部, 教授 (00038093)
キーワード	分子場 / 反応場 / 包接結晶反応 / マトリックス / 生体反応モデル / 不斉反応
研究概要	本研究は昨年度と同様、大きく4つのグル-プに分けて行なわれた。第1グル-プは、特異な集合分子場の設計による物質変換について研究した。α‐オキソアミドの包接結晶中の光反応、フェナントレンおよびチエノアセン骨格が作る包接結晶中の光ソルボリシス、液晶性ジアセチレンの重合挙動、包接体結晶場でのシクロヘキセノンの光付加反応、キンヒドロン系を用いる新しいプロトン‐電子連動システムの開発、含硫および含窒素[7]アヌレン化合物の合成と反応などが検討され、包接結晶場、液晶などの秩序場での特異な反応性が示された。第2グル-プは、生体分子場のモデルの設計と物質変換について研究した。フェノ-ル、イミダゾ-ル骨格をもつ二官能性触媒による核酸の解裂、光合成モデル系における電子移動に及ぼす発色団の配向効果、視物質作用モデルとしての蛋白質分子場におけるポリエナ-ルの立体特異的異性化、含セレンホスト分子を利用した特異な電子伝達系の機能設計、ビナフタレン不斉分子認識場をもつ酵素モデル触媒による一酸素添加反応について研究した。第3グル-プは、特異な単分子場の設計による物質変換について研究した。アルゴン、酸素、有機マトリックス中での二価活性種、酸素活性種の発生と物質変換、電場下での特異なトリフルオロメチル化、極めてかさ高い置換基を分子場とする活性種の安定化、遷移金属の配位子場による含カルコゲン錯体の合成、不斉反応、高配位有機ケイ素場による新規合成法の開発を研究し、巧妙に設計された単一の分子が特異な分子場を提供できることがわかった。第4グル-プは、分子場設計を物理化学的側面から検討した。シアノエチル基をもつコバロキシムにおいて、ラセミ結晶の光照射でキラル化が起ることがX線結晶解析で示された。Si_<60>、Si_<24>、Si_<60>H_<60>などのケイ素クラスタ-の理論計算から、これらが炭素クラスタ-と異なる興味ある性質をもつことが示された。

研究成果
(22件)

すべてその他

すべて文献書誌 (22件)

[文献書誌] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Matsuhashi,and R.Okazaki: "1,2,3,4,5‐Tetrathiametallolanes of Group 14 Metals,RR'MS_4(M=Si,Ge,and Sn): Synthesis and Crystal Structures." J.Am.Chem.Soc.113. 7047-7049 (1991)
[文献書誌] M.Sakamoto,S.Watanabe,T.Fujita,H.Aoyama,and Y.Omote: "Photochemical Reactions of N‐Acyldithiocarbamates and N‐Acylthiocarbamates." J.Chem.Soc.Perkin Trans.1. 2541-2545 (1991)
[文献書誌] T.Motomura and Y.Aoyama: "Accumulation of Hydrogen‐Bonding and Electrostatic Binding Sites: Stabilization of Salts in Hydroxylic Media via Intramolecular Hydrogen‐Bonding." J.Org.Chem.56. 7224-7228 (1991)
[文献書誌] T.Akasaka,K.Sato,M.Kako,and W.Ando: "Formation of 1,2,3,6‐Dioxadisilene in Photo‐induced Electron Transfer Oxygenation of 1,2‐Disiletene." Tetrahedorn Lett.32. 6605-6608 (1991)
[文献書誌] M.Sakurada,M.Kajitani,K.Dohki,T.Akiyama,and A.Sugimori: "Reactions of Dithiolenes with Diazo Compounds: Cycloaddition and Dissociation of Alkylidene Groups." J.Organomet.Chem.423. 141-161 (1992)
[文献書誌] K.Uneyama and M.Kanai: "Generation of Perfluoroalkyl Radicals at Low Temperature by Tellurolate Mediated Electron Transfer." Tetrahedron Lett.32. 7425-7428 (1991)
[文献書誌] Y.T.Osano,A.Uchida,and Y.Ohashi: "Optical Enrichment of a Racemic Chiral Crystal by X‐ray Irradiation." Nature(London). 352. 510-512 (1991)
[文献書誌] M.Kira,T.Maruyama,and H.Sakurai: "The First Matrix‐Isolation and Electronic Structure of Vinyl‐Substituted Silylenes." Tetrahedron Lett.33. 243-246 (1992)
[文献書誌] Y.Mazaki,S.Murata,and K.Kobayashi: "Thermal and Photochemical Formation of Quinonoid Derivatives of Condensed Polythiophenes and Their Spectral Properties." Tetrahedron Lett.32. 4367-4370 (1991)
[文献書誌] Y.Sakata,H.Tsue,Y.Goto,S.Misumi,T.Asahi,T.Nishikawa,T.Okada,N.Mataga: "Observation of Large Orientation Effect on Photoinduced Electron Transfer in Rigid Porphyrin‐Quinone Compounds." Chem.Lett.1991. 1307-1310 (1991)
[文献書誌] R.Akaba,H.Sakuragi,and K.Tokumaru: "Detection of Dimeric Cation Radicals of Trans‐stilbene in 2,4,6‐triphenylpyrylium Tetrafluoroborate‐sensitized Electron Transfer Reactions in Dichloromethane." Chem.Phys.Lett.174. 80-84 (1990)
[文献書誌] A.Miyazaki,A.Izuoka,and T.Sugawara: "Structure of 11,12‐Bis(diazo)‐11,12‐dihydroindeno[2,1‐a]fluorene" Acta Cryst.C47. 1054-1056 (1991)
[文献書誌] X.Zhang,K.Mashima,K.Koyano,N.Sayo,H.Kumobayashi,S.Akutagawa,and H.Takaya: "Synthesis of Partially Hydrogenated BINAP Variants." Tetrahedron Lett.32. 7283-7286 (1991)
[文献書誌] F.Toda and K.Tanaka: "Optical Resolution of Bicyclo[2.2.1]heptanone,Bicyclo[2.2.2]‐octanone,and Bicyclo[3.2.1]octanone Derivatives by Inclusion Complexation with Optically Active Host Compounds." J.Org.Chem.56. 7332-7335 (1991)
[文献書誌] M.Yoneda,K.Tsujimoto,M.Ohashi,M.Shiratsuchi,Y.Ohkawa,and K.Isa: "Fast Atom Bombardment Mass Spectra of the β‐Blocker Nipradilol with Nitratye Ester Group‐Tandem Mass Spectrometory(MS/MS)and B/E Constant Linked Scanning." Chem.Pharm.Bull.38. 3389-3394 (1990)
[文献書誌] S.Murata and H.Tomioka: "Photochemistry of o‐Nitrophenylazide in Matrices. The First Direct Spectroscopic Observation of o‐Dinitrosobenzene." Chem.Lett.1992. 57-60 (1992)
[文献書誌] M.Iwaoka and S.Tomoda: "Direct Observation of Intramolecular Interaction Between a Divalent Selenium and a tertiary Amine by Means of Single Crystal X‐ray Analysis and NMR Spectroscopy." Phosphorus,Sulfer,and Silicon and The Related Elements.
[文献書誌] S.Nagase and K.Kobayashi: "Si_<60> and Si_<60>X(X=Ne,F^-,and Na^+)" Chem.Phys.Lett.187. 291-294 (1991)
[文献書誌] K.Nishino,M.Takagi,T.Kawata,I.Murata,J.Inanaga,and K.Nakasuji: "Thiepin‐iron Tricarbonyl: Stabilization of Thermally Labile Parent Thiepin by Transition Metal Complexzation." J.Am.Chem.Soc.113. 5059-5060 (1991)
[文献書誌] M.Nakamura and N.Nakamura: "Spin State and Rotational Orientation of Iron Porphyrin Complexes with Hindered 2‐Methylbenzimidazole as Axial Ligands." Chem.Lett.1991. 1885-1888 (1991)
[文献書誌] Y.Naruta and K.Maruyama: "High Oxygen‐Evolving Activity of Rigidly Linked Manganese(III)Porphyrin Dimers. A Functional Madel of Mangenese Catalase." J.Am.Chem.Soc.113. 3595-3596 (1991)
[文献書誌] T.Machiguchi,Y.Kano,and T.Hasegawa: "General and Facile Synthesis of 2‐Substituted Tropothiones." Chem.Lett.1990. 1563-1566 (1990)

1991 年度 実績報告書

特異な分子場の設計に基づく物質変換

研究代表者

岡崎 廉治 東京大学, 理学部, 教授 (70011567)

研究成果

[文献書誌] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Matsuhashi,and R.Okazaki: "1,2,3,4,5‐Tetrathiametallolanes of Group 14 Metals,RR'MS_4(M=Si,Ge,and Sn): Synthesis and Crystal Structures." J.Am.Chem.Soc.113. 7047-7049 (1991)

[文献書誌] M.Sakamoto,S.Watanabe,T.Fujita,H.Aoyama,and Y.Omote: "Photochemical Reactions of N‐Acyldithiocarbamates and N‐Acylthiocarbamates." J.Chem.Soc.Perkin Trans.1. 2541-2545 (1991)

[文献書誌] T.Motomura and Y.Aoyama: "Accumulation of Hydrogen‐Bonding and Electrostatic Binding Sites: Stabilization of Salts in Hydroxylic Media via Intramolecular Hydrogen‐Bonding." J.Org.Chem.56. 7224-7228 (1991)

[文献書誌] T.Akasaka,K.Sato,M.Kako,and W.Ando: "Formation of 1,2,3,6‐Dioxadisilene in Photo‐induced Electron Transfer Oxygenation of 1,2‐Disiletene." Tetrahedorn Lett.32. 6605-6608 (1991)

[文献書誌] M.Sakurada,M.Kajitani,K.Dohki,T.Akiyama,and A.Sugimori: "Reactions of Dithiolenes with Diazo Compounds: Cycloaddition and Dissociation of Alkylidene Groups." J.Organomet.Chem.423. 141-161 (1992)

[文献書誌] K.Uneyama and M.Kanai: "Generation of Perfluoroalkyl Radicals at Low Temperature by Tellurolate Mediated Electron Transfer." Tetrahedron Lett.32. 7425-7428 (1991)

[文献書誌] Y.T.Osano,A.Uchida,and Y.Ohashi: "Optical Enrichment of a Racemic Chiral Crystal by X‐ray Irradiation." Nature(London). 352. 510-512 (1991)

[文献書誌] M.Kira,T.Maruyama,and H.Sakurai: "The First Matrix‐Isolation and Electronic Structure of Vinyl‐Substituted Silylenes." Tetrahedron Lett.33. 243-246 (1992)

[文献書誌] Y.Mazaki,S.Murata,and K.Kobayashi: "Thermal and Photochemical Formation of Quinonoid Derivatives of Condensed Polythiophenes and Their Spectral Properties." Tetrahedron Lett.32. 4367-4370 (1991)

[文献書誌] Y.Sakata,H.Tsue,Y.Goto,S.Misumi,T.Asahi,T.Nishikawa,T.Okada,N.Mataga: "Observation of Large Orientation Effect on Photoinduced Electron Transfer in Rigid Porphyrin‐Quinone Compounds." Chem.Lett.1991. 1307-1310 (1991)

[文献書誌] R.Akaba,H.Sakuragi,and K.Tokumaru: "Detection of Dimeric Cation Radicals of Trans‐stilbene in 2,4,6‐triphenylpyrylium Tetrafluoroborate‐sensitized Electron Transfer Reactions in Dichloromethane." Chem.Phys.Lett.174. 80-84 (1990)

[文献書誌] A.Miyazaki,A.Izuoka,and T.Sugawara: "Structure of 11,12‐Bis(diazo)‐11,12‐dihydroindeno[2,1‐a]fluorene" Acta Cryst.C47. 1054-1056 (1991)

[文献書誌] X.Zhang,K.Mashima,K.Koyano,N.Sayo,H.Kumobayashi,S.Akutagawa,and H.Takaya: "Synthesis of Partially Hydrogenated BINAP Variants." Tetrahedron Lett.32. 7283-7286 (1991)

[文献書誌] F.Toda and K.Tanaka: "Optical Resolution of Bicyclo[2.2.1]heptanone,Bicyclo[2.2.2]‐octanone,and Bicyclo[3.2.1]octanone Derivatives by Inclusion Complexation with Optically Active Host Compounds." J.Org.Chem.56. 7332-7335 (1991)

[文献書誌] M.Yoneda,K.Tsujimoto,M.Ohashi,M.Shiratsuchi,Y.Ohkawa,and K.Isa: "Fast Atom Bombardment Mass Spectra of the β‐Blocker Nipradilol with Nitratye Ester Group‐Tandem Mass Spectrometory(MS/MS)and B/E Constant Linked Scanning." Chem.Pharm.Bull.38. 3389-3394 (1990)

[文献書誌] S.Murata and H.Tomioka: "Photochemistry of o‐Nitrophenylazide in Matrices. The First Direct Spectroscopic Observation of o‐Dinitrosobenzene." Chem.Lett.1992. 57-60 (1992)

[文献書誌] M.Iwaoka and S.Tomoda: "Direct Observation of Intramolecular Interaction Between a Divalent Selenium and a tertiary Amine by Means of Single Crystal X‐ray Analysis and NMR Spectroscopy." Phosphorus,Sulfer,and Silicon and The Related Elements.

[文献書誌] S.Nagase and K.Kobayashi: "Si_<60> and Si_<60>X(X=Ne,F^-,and Na^+)" Chem.Phys.Lett.187. 291-294 (1991)

[文献書誌] K.Nishino,M.Takagi,T.Kawata,I.Murata,J.Inanaga,and K.Nakasuji: "Thiepin‐iron Tricarbonyl: Stabilization of Thermally Labile Parent Thiepin by Transition Metal Complexzation." J.Am.Chem.Soc.113. 5059-5060 (1991)

[文献書誌] M.Nakamura and N.Nakamura: "Spin State and Rotational Orientation of Iron Porphyrin Complexes with Hindered 2‐Methylbenzimidazole as Axial Ligands." Chem.Lett.1991. 1885-1888 (1991)

[文献書誌] Y.Naruta and K.Maruyama: "High Oxygen‐Evolving Activity of Rigidly Linked Manganese(III)Porphyrin Dimers. A Functional Madel of Mangenese Catalase." J.Am.Chem.Soc.113. 3595-3596 (1991)

[文献書誌] T.Machiguchi,Y.Kano,and T.Hasegawa: "General and Facile Synthesis of 2‐Substituted Tropothiones." Chem.Lett.1990. 1563-1566 (1990)

1991 年度実績報告書

岡崎廉治東京大学, 理学部, 教授 (70011567)