1992 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) 竹下斉九州大学, 機能物質科学研究所, 教授 (70004281)
Keywords	超高圧反応 / クラウンエーテル / 超音波化学 / フラッシュ気相熱分解 / プラズマ / カルベル / 固相反応 / ヌクレオシド
Research Abstract	1.超高圧環境では,エステルの加水分解反応における無触媒化,イミンのヘテロ・ディールスアルダー反応による抗HIV活性を持つヌクレシドの合成,特異共役化合物の環化付加反応による新規化合物の合成,さらには,芳香族求核置換反応による銀特異的クラウンエーテルの合成などの成果を挙げている。 2.超音波環境では,塩酸処理シリカゲルでのスルフィドから塩化スルホニルの効率的合成,有機結晶相での基礎的有機反応の超音波効果,リボヌクレオシドの還元による高選択的デオキシリボヌクレオシドの合成,固体ポリ塩化ビニルとスチレンモノマーのメカノケミカル・ブロック共重合反応の機作,および超音波による細胞の物理的致死損傷と化学的致死損傷との同時誘超などユニークな興味ある結果が得られている。 3.フラッシュ気相熱分解の分野では,メトキシカルボニル基などの官能基を有するフェニルカルベンを高温気相中で発生させたところ官能基とカルベンとの相互作用のパターンが室温液相中でのそれと全く異なるという知見が符ろれている。また,単体硫黄とシラン化合物との高温反応ではS_i-S-S_i結合が生成し,初めてカゴ型ケイ素化合物が得られた。そのほか,縮環シクロブテンの高温反応においても予想外の興味ある反応が見出された。 4.プラズマによる分子の活性化では,まずプラズマによるシクロアルカンの酸化があり,またプラズマ環境下ヨウ素ガスを導入してヨウ素分子を活性化させて高分子材料表面のヨウ素化と機能化とが可能であることを明らかにした。

Research Products
(20 results)

All Other

All Publications (20 results)

[Publications] Kiyoshi MATSUMOTO: "Synthesis of Functionalized Pyridines By Aminolysis of 2,6-Dichlopyridines" Chemistry Express. 7. 473-476 (1992)
[Publications] Kaoru Fuji: "DIASTEREOSELECTIVE DIELS-ALDER REACTIONS WITH CHIRAL SULFINYL DEROVATOVES AS DIENOPHILES UNDER HIGH ORESSURE" Tetrahedron:Asymmetry. 3. 609-612 (1992)
[Publications] Nobuya KATAGIRI: "Synthesis of Nucleosides and Related Compounds XXVI.The Difference in Effect between High Pressure and LiClO_4the Diels-Alder Reaction of Cyclopentadiene with methylenemalonates or ο-Acetylisonitrosomalonates" Chem.Pharm.Bull.40. 1737-1741 (1992)
[Publications] Yoshinori YAMAMOTO: "Cleavage of esters under Nearly Neutral Conditions at High Pressure.Chemand Regioselective Hydrolysis in Organic Solvents" J.Org.Chem.56. 5737-5738 (1991)
[Publications] Toshikazu IBATA: "Aromatic Nucleophilic Substitution of Halobenzenes with Amines under High Pressure" Bull.Chem.Soc.Jpn.64. 42-49 (1991)
[Publications] Hitoshi TAKESHITA: "High-Pressure Cycloaddition of Cycloheptatriene to 1,4-Dimethyl-7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dioate" Chem.Express. 8. 109-112 (1993)
[Publications] E.Kawashima: "Sonochemical and Triethylborane-induced Tin Deuteride for the Highly Stereoselectivite Synthesis of (2'R)-[2'-2H]-2'-Deoxyribonucleosides from 2'-Functionalized Ribonucleosides" Terahedron Lett.34. (1993)
[Publications] Hajime SOHMIYA: "Novel One-Pot Synthesis of Sulfonyl Chlorides from Sulfides with Iodosobenzene and Hydrogen Chloride-Treated Silica Gel" Chem.Lett.891-892 (1992)
[Publications] Sei-ichi NISHIMOTO: "1-(5'-Fluoro-6'-hydroxy-5',6'-dihydrouracil-5'-yl)-5-fluorouracil,a Novel N(1)-C(5)-Linked Dimer That Release 5-Fluorouracil by Radiation Activation under Hypoxic Conditions" J.Med.Chem.35. 2711-2712 (1992)
[Publications] Hideki FUJIWARA: "Mechanochemical Block Copolymerization in Heterogeneous Systems of the Solid Poly(vinyl chloride)with Styrene by Ultrasonic Irradiation" Polymer Bull.28. 189-196 (1992)
[Publications] Takashi AKASAKA: "Photo-induced Electron Transfer Oxygenation of 1,2-Disiletene" Tetrahedron. 48. 3283-3292 (1992)
[Publications] Junko ICHHARA: "Acceleration of the fluorination of Benzy Halide by the Combination of Lead Fluoride and Sodium Salt" Chem.Lett.1161-1164 (1992)
[Publications] Hideo TOMIOKA: "Intervention of Carbonyl and Oxonium Yiles in Reactions of [(Alkoxycarbonyl)phenyl]carbenes inb the Gas Phase Forming 3-Alkylphtalides and 2-Alkoxy-1(2Η)-benzocyclobutenone. ^<13>Cand ^<18>OLabeling Studies" J.Am.Chem.Soc.113. 8771-8778 (1991)
[Publications] Takeshi KAWASE: "Synthesis and Alkari Metal Reduction of 1,1-Diarylspiro[2,4]hepta-4,6-diene.Generation of Homopentafulvene Dianions" Tetrahedron Lett.33. 7201-7204 (1992)
[Publications] Meguru TEZUKA: "Oxidation of Cycloalkanes in a Radiofrequency Plasma" Bull.chem.Soc.Jpn.64. 1063-1065 (1991)
[Publications] 青柿良一: "バイオセンサー用白金微小電極の作成" 技術・教育研究論文誌. 1. 123-128 (1992)
[Publications] 石神正浩: "熱水噴出孔モデル実験と化学進化" 海洋. 24. 741-748 (1992)
[Publications] Koichi Tanaka: "Regio-and Enantio-selective Photodimerisation of Cyclohex-2-enone as an lnclusion Complex with a New Optically Active Host,(-)-1,4-Bis[3-(ο-chlorophenyl)-3-hydroxy-3-phenylprop-1-ynyl]benzene:Preparation of the Optically Pure(-)-syn-trans-Dimer of Cyclohex-2-enone" J.CHEM.SOC.PERKIN TRANS.1. 307-308 (1992)
[Publications] Kuniaki ITOH: "The Photoaddition of Enaminoketonatoboron Difluorides with trans-Stilbene" J.Chem.Soc.,Chem.Commun.1608-1609 (1992)
[Publications] Kiyoshi MATSUMOTO: "High Pressure Functionalization of Diaza-Crown Ethers and Thioethers" High Pressure Research. (1992)

1992 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: "Synthesis of Functionalized Pyridines By Aminolysis of 2,6-Dichlopyridines" Chemistry Express. 7. 473-476 (1992)

[Publications] Kaoru Fuji: "DIASTEREOSELECTIVE DIELS-ALDER REACTIONS WITH CHIRAL SULFINYL DEROVATOVES AS DIENOPHILES UNDER HIGH ORESSURE" Tetrahedron:Asymmetry. 3. 609-612 (1992)

[Publications] Nobuya KATAGIRI: "Synthesis of Nucleosides and Related Compounds XXVI.The Difference in Effect between High Pressure and LiClO_4the Diels-Alder Reaction of Cyclopentadiene with methylenemalonates or ο-Acetylisonitrosomalonates" Chem.Pharm.Bull.40. 1737-1741 (1992)

[Publications] Yoshinori YAMAMOTO: "Cleavage of esters under Nearly Neutral Conditions at High Pressure.Chemand Regioselective Hydrolysis in Organic Solvents" J.Org.Chem.56. 5737-5738 (1991)

[Publications] Toshikazu IBATA: "Aromatic Nucleophilic Substitution of Halobenzenes with Amines under High Pressure" Bull.Chem.Soc.Jpn.64. 42-49 (1991)

[Publications] Hitoshi TAKESHITA: "High-Pressure Cycloaddition of Cycloheptatriene to 1,4-Dimethyl-7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dioate" Chem.Express. 8. 109-112 (1993)

[Publications] E.Kawashima: "Sonochemical and Triethylborane-induced Tin Deuteride for the Highly Stereoselectivite Synthesis of (2'R)-[2'-2H]-2'-Deoxyribonucleosides from 2'-Functionalized Ribonucleosides" Terahedron Lett.34. (1993)

[Publications] Hajime SOHMIYA: "Novel One-Pot Synthesis of Sulfonyl Chlorides from Sulfides with Iodosobenzene and Hydrogen Chloride-Treated Silica Gel" Chem.Lett.891-892 (1992)

[Publications] Sei-ichi NISHIMOTO: "1-(5'-Fluoro-6'-hydroxy-5',6'-dihydrouracil-5'-yl)-5-fluorouracil,a Novel N(1)-C(5)-Linked Dimer That Release 5-Fluorouracil by Radiation Activation under Hypoxic Conditions" J.Med.Chem.35. 2711-2712 (1992)

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

[Publications] Takashi AKASAKA: "Photo-induced Electron Transfer Oxygenation of 1,2-Disiletene" Tetrahedron. 48. 3283-3292 (1992)

[Publications] Junko ICHHARA: "Acceleration of the fluorination of Benzy Halide by the Combination of Lead Fluoride and Sodium Salt" Chem.Lett.1161-1164 (1992)

[Publications] Hideo TOMIOKA: "Intervention of Carbonyl and Oxonium Yiles in Reactions of [(Alkoxycarbonyl)phenyl]carbenes inb the Gas Phase Forming 3-Alkylphtalides and 2-Alkoxy-1(2Η)-benzocyclobutenone. ^<13>Cand ^<18>OLabeling Studies" J.Am.Chem.Soc.113. 8771-8778 (1991)

[Publications] Takeshi KAWASE: "Synthesis and Alkari Metal Reduction of 1,1-Diarylspiro[2,4]hepta-4,6-diene.Generation of Homopentafulvene Dianions" Tetrahedron Lett.33. 7201-7204 (1992)

[Publications] Meguru TEZUKA: "Oxidation of Cycloalkanes in a Radiofrequency Plasma" Bull.chem.Soc.Jpn.64. 1063-1065 (1991)

[Publications] 青柿 良一: "バイオセンサー用白金微小電極の作成" 技術・教育研究論文誌. 1. 123-128 (1992)

[Publications] 石神 正浩: "熱水噴出孔モデル実験と化学進化" 海洋. 24. 741-748 (1992)

[Publications] Kuniaki ITOH: "The Photoaddition of Enaminoketonatoboron Difluorides with trans-Stilbene" J.Chem.Soc.,Chem.Commun.1608-1609 (1992)

[Publications] Kiyoshi MATSUMOTO: "High Pressure Functionalization of Diaza-Crown Ethers and Thioethers" High Pressure Research. (1992)

松本澄京都大学, 大学院人間・環境学研究科, 教授 (20026818)

[Publications] 青柿良一: "バイオセンサー用白金微小電極の作成" 技術・教育研究論文誌. 1. 123-128 (1992)

[Publications] 石神正浩: "熱水噴出孔モデル実験と化学進化" 海洋. 24. 741-748 (1992)