1993 Fiscal Year Annual Research Report

極限環境における分子の活性化と反応の制御

Research Project

Project/Area Number	04303003
Research Institution	KYOTO UNIVERSITY
Principal Investigator	松本澄京都大学, 大学院・人間・環境学研究科, 教授 (20026818)
Co-Investigator(Kenkyū-buntansha)	中村栄一東京工業大学, 理学部, 教授 (00134809) 富岡秀雄三重大学, 工学部, 教授 (20024599) 安藤亘筑波大学, 化学系, 教授 (30008429) 安藤喬志滋賀医科大学, 医学部, 教授 (70029867) 竹下齊九州大学, 機能物質科学研究所, 教授 (70004281)
Keywords	超高圧反応 / 超音波化学 / フラッシュ気相熱分解 / プラズマ / カルベン / 固相反応 / ヌクレオシド / フラーレン
Research Abstract	本研究の概要を各分科会ごとにまとめた。 [超高圧]:超高圧を用いる理由は通常条件で当該の反応が使えないからである。各分担者はそれぞれの必要性から超高圧環境を用いてヌクレオシド系抗HIV剤(±)-BCAの酵素的光学分割(金子)、中性に近い条件でのエステルの開裂(山本)、超高圧条件下でのダイナミックな溶媒効果の研究(原)、モノ及び多塩素置換ニトロベンゼン類の芳香族求核置換反応(井畑)、フラーレン(C_<60>)とトロポンのDiels-Alder反応(竹下)、銀選択性アザクラウンエーテル類の合成(松本)を行った。 [超音波]:超音波が有機反応に影響を与える機構は良く分かっていないが、均一、不均一を問わず溶液中で特異な現象がしばしば見いだされた。成果としては、オレフィンのヒドロキシスタネーション(中村)、光化学反応との併用の試み(安藤_喬)、既知反応による超音波環境下の反応メカニズムの研究(木村)、生体物質への超音波環境の影響(西本)、超音波環境下での高分子化合物の改質(藤原)、結晶中での有機反応(戸田)、固-液界面でのフッ素化反応(市原)がもたらされた。 [閃光熱分解(FVP)]:FVPは不活性ガス気流下あるいは低圧下で専ら分子内熱分解反応により、通常条件下で合成するのが困難な化合物を得ようとする方法である。分担者の主な成果は、シリコンやゲルマニウムなどの14族不飽和化合物の分子内反応(安藤_亘)ジフェニルカルベンの転移反応(富岡)、6-(2-チエニル)ペンタフルバレンオリゴマーの合成(小田)であった。 [プラズマ]:有機反応に用いる低温プラズマ状態とは有機モノマーガスのグロー放電により生じる数万℃の電子温度と、数百℃のガス温度の熱的非平衡状態で、通常の条件とは全く違った、電気当量に従わない連鎖反応などがおこる。この分科会の成果としては、水溶液、有機溶液でのグロー放電電解(CGDE)(手塚)、機能性有機薄膜の合成(吉田)、熱水噴出孔モデルと化学進化(石神)がある。

Research Products
(19 results)

All Other

All Publications (19 results)

[Publications] Kiyoshi Matsumoto: "High Pressure Synthesis of Functionalized Monoaza-Crown Ethers That Show Specific Binding Properties for Ag^+ Ion" Chemistry Express. 8. 105-108 (1993)
[Publications] Mitsuo Toda: "Synthesis of Metal Ion-Specific Bindings of New Functionalized Aza-Crown Ethers" Supramolecular Chemistry. 2. 289-293 (1993)
[Publications] Nobuya Katagiri: "Resolution of 9-[c-4,t-5-Bis(hydroxymethyl)cyclopent-2-en-r-1-yl]-9H-adenine[(±)-BCA] by Means of High-Pressure-Mediated Deamination with Adenosine Deaminase" Chem.Pharm.Bull.41. 1027-1029 (1993)
[Publications] Toshiaki Furuta: "Cleavage of Esters under Nearly Neutral Conditions at High Pressure" High Pressure Research. 11. 93-106 (1992)
[Publications] Kimihiko Hara: "Effect of Presure on the Fluorescence of TICT States in (N,N--Dimethylamino)-benzonitrile and Its Related Compounds" J.Phys.Chem.96. 8307-8309 (1992)
[Publications] Toshikazu Ibata: "Nitro Group Substitution Reaction of 2,3,5,6-Tetrachloronitrobenzene with Primary and Secondary Amines under High Pressure" Tetrahedron Lett.34. 5613-5614 (1993)
[Publications] Akira Sera: "Norrish Type II Photo-Deacylation of Semicyclic Imides" Heterocycles. 36. 1039-1046 (1993)
[Publications] Hitoshi Takeshita: "High-Pressure Diels-Aldes Reaction between Buckminsterfullerene and Tropone" Chem.Lett.1697-1698 (1993)
[Publications] Takahide Kimura: "Selectivity in Catlytic Dehydrogenation with Active Manganese Dioxide" Bull.Chem.Soc.Jpn.65. 1749-1750 (1992)
[Publications] Bunsho Ohtani: "Effect of Surface Adsorptions of Aliphatic Alcohols and Silver Ion on the Photocatalitic Activity of TiO_2Suspended in Aqueous Solutons" J.Phys.Chem.97. 920-926 (1993)
[Publications] Hideki Fujiwara: "Mechanochemical Block Copolymerization in Heterogeneous System of the Solid Poly(vinyl chloride) with Styrene by Ultrasonic Irradiation" Polymer Bulletin. 28. 189-196 (1992)
[Publications] Fumio Toda: "Some Enantioselective Photocyclization Reaction in Inclusion Crystal with Optically Active Host Compounds" J.Org.Chem.58. 6208-6211 (1993)
[Publications] Junko Ichihara: "Acceralation of the Fluorination of Benzyl Halide by the Combination of Lead Fluoeide and Sodium Salt" Chemistry Lett.ers. 1161-1164 (1992)
[Publications] Nami Choi: "Synthesis and Reactions of 2-Alkylidene-1,3,4-thiadiazolinines and Their Selenium Analogues" Tetrahedron. 49. 1189-1202 (1993)
[Publications] Hideo Tomioka: "Formation of Heptafulvene in Reaction of[(Methoxycarbonyl)methyl]phenylcarbene in the Gas Phases" J.Org.Chem.58. 4196-4197 (1993)
[Publications] Takeshi Kawase: "Synthesis and Properties of Oligo-6-(2-thienyl)pentafulvenes" Tetrahedron Lett.34. 3449-3452 (1993)
[Publications] Meguru Tezuka: "Anodic Hydrogen Evolution in Contact Glow-Discharge Electrolysis of Sulfuric Acid Solution" Denki Kagaku. 61. 794-795 (1993)
[Publications] 石神正浩: "熱水噴出孔モデル実験と化学進化" 海洋. 24. 741-743 (1992)
[Publications] Yasuhiko Yoshida: "New Functionality Materials,Volume C:Synthetic Process and Control of Functionality Materials" Esevier Science Publishers,B.V., 449-454 (1993)

1993 Fiscal Year Annual Research Report

極限環境における分子の活性化と反応の制御

Principal Investigator

松本 澄 京都大学, 大学院・人間・環境学研究科, 教授 (20026818)

Research Products

[Publications] Kiyoshi Matsumoto: "High Pressure Synthesis of Functionalized Monoaza-Crown Ethers That Show Specific Binding Properties for Ag^+ Ion" Chemistry Express. 8. 105-108 (1993)

[Publications] Mitsuo Toda: "Synthesis of Metal Ion-Specific Bindings of New Functionalized Aza-Crown Ethers" Supramolecular Chemistry. 2. 289-293 (1993)

[Publications] Nobuya Katagiri: "Resolution of 9-[c-4,t-5-Bis(hydroxymethyl)cyclopent-2-en-r-1-yl]-9H-adenine[(±)-BCA] by Means of High-Pressure-Mediated Deamination with Adenosine Deaminase" Chem.Pharm.Bull.41. 1027-1029 (1993)

[Publications] Toshiaki Furuta: "Cleavage of Esters under Nearly Neutral Conditions at High Pressure" High Pressure Research. 11. 93-106 (1992)

[Publications] Kimihiko Hara: "Effect of Presure on the Fluorescence of TICT States in (N,N--Dimethylamino)-benzonitrile and Its Related Compounds" J.Phys.Chem.96. 8307-8309 (1992)

[Publications] Toshikazu Ibata: "Nitro Group Substitution Reaction of 2,3,5,6-Tetrachloronitrobenzene with Primary and Secondary Amines under High Pressure" Tetrahedron Lett.34. 5613-5614 (1993)

[Publications] Akira Sera: "Norrish Type II Photo-Deacylation of Semicyclic Imides" Heterocycles. 36. 1039-1046 (1993)

[Publications] Hitoshi Takeshita: "High-Pressure Diels-Aldes Reaction between Buckminsterfullerene and Tropone" Chem.Lett.1697-1698 (1993)

[Publications] Takahide Kimura: "Selectivity in Catlytic Dehydrogenation with Active Manganese Dioxide" Bull.Chem.Soc.Jpn.65. 1749-1750 (1992)

[Publications] Bunsho Ohtani: "Effect of Surface Adsorptions of Aliphatic Alcohols and Silver Ion on the Photocatalitic Activity of TiO_2Suspended in Aqueous Solutons" J.Phys.Chem.97. 920-926 (1993)

[Publications] Hideki Fujiwara: "Mechanochemical Block Copolymerization in Heterogeneous System of the Solid Poly(vinyl chloride) with Styrene by Ultrasonic Irradiation" Polymer Bulletin. 28. 189-196 (1992)

[Publications] Fumio Toda: "Some Enantioselective Photocyclization Reaction in Inclusion Crystal with Optically Active Host Compounds" J.Org.Chem.58. 6208-6211 (1993)

[Publications] Junko Ichihara: "Acceralation of the Fluorination of Benzyl Halide by the Combination of Lead Fluoeide and Sodium Salt" Chemistry Lett.ers. 1161-1164 (1992)

[Publications] Nami Choi: "Synthesis and Reactions of 2-Alkylidene-1,3,4-thiadiazolinines and Their Selenium Analogues" Tetrahedron. 49. 1189-1202 (1993)

[Publications] Hideo Tomioka: "Formation of Heptafulvene in Reaction of[(Methoxycarbonyl)methyl]phenylcarbene in the Gas Phases" J.Org.Chem.58. 4196-4197 (1993)

[Publications] Takeshi Kawase: "Synthesis and Properties of Oligo-6-(2-thienyl)pentafulvenes" Tetrahedron Lett.34. 3449-3452 (1993)

[Publications] Meguru Tezuka: "Anodic Hydrogen Evolution in Contact Glow-Discharge Electrolysis of Sulfuric Acid Solution" Denki Kagaku. 61. 794-795 (1993)

[Publications] 石神 正浩: "熱水噴出孔モデル実験と化学進化" 海洋. 24. 741-743 (1992)

[Publications] Yasuhiko Yoshida: "New Functionality Materials,Volume C:Synthetic Process and Control of Functionality Materials" Esevier Science Publishers,B.V., 449-454 (1993)

松本澄京都大学, 大学院・人間・環境学研究科, 教授 (20026818)

[Publications] 石神正浩: "熱水噴出孔モデル実験と化学進化" 海洋. 24. 741-743 (1992)