1997 年度実績報告書

極限反応場での物質変換新手法

研究課題

研究課題/領域番号	07304047
研究機関	高知大学
研究代表者	小槻日吉三高知大学, 理学部, 助教授 (80093954)
研究分担者	西本清一京都大学, 大学院・工学研究科, 教授 (10115909) 富岡秀雄三重大学, 工学部, 教授 (20024599) 浅野努九州大学, 有機化学基礎研究センター, 教授 (40094057) 森章九州大学, 機能物質科学研究所, 教授 (70038602) 松本澄京都大学, 大学院・人間環境学研究科, 教授 (20026818)
キーワード	有機合成 / 超高圧反応 / 超音波 / フラッシュ気相熱分解 / プラズマ / ラジカル反応 / 有機官能基変換 / 極限反応
研究概要	本研究では、超高圧・超音波・フラッシュ気相熱分解(FVP:有機化合物にとっての超高温)の三つの超条件に加え、プラズマの極限条件を用いる新しい有機化合物の活性化を達成し、それによる有機化合物の効率的な変換を行うことを目的とした。個々の分野での具体的な成果は次の通りである。 1.超高圧条件下での有機合成: 超高圧反応場での分子認識能を有する超分子化合物の合成、芳香族求核置換反応による芳香族アミンの類の新規合成、酵素の活性化による核酸物質の変換、トロポロン類の新規環状付加反応、有機異性化反応の圧力効果と機構の解明、β-ケトエステル類のマイケル反応に対する高圧反応及びシリカゲル触媒の有用性、さらにはいくつかの新規官能基変換反応の開発。 2.超音波環境下での有機合成: 超音波照射条件の実験的制御と画一的に配慮しつつ、固相反応への超音波の効果、超音波環境下におけるフッ素化、フルオロウラシル類の超音波活性化プロドラッグ化、水溶媒の反応への影響、活性酸素発生機構の解明。あわせて、それらの反応機構の解析や分子変換。 3.フラッシュ気相熱分解(FVP): カルベン・ナイトレン等の高温気相下での反応・機構の解明、有機ケイ素・ゲルマニウム化合物の新規反応性の開発による環状新規化合物の合成。 4.プラズマ有機合成放電条件の違いにより発生するプラズマの状態に相違があるが、有機化合物の新規変換を目標として、グロー放電法による新規ラジカル種の生成、医薬品関連高分子化合物の表面処理技術への適用、固体バ-オキシラジカルの構造と反応性の解明。

研究成果

(20件)

すべてその他

すべて文献書誌 (20件)

[文献書誌] H.Kotsuki: "A New Facile Method for the Chemoselective Roductive Transformafion of Azides to N-(tert-Batoxycarbonyl)amines" Jetrahedron Letlers. 38. 2129-2132 (1997)
[文献書誌] H.Kotsuki: "Yb(orf)_3-Catalyzed Michael Addition Reactions of β-Ketoesters on Silica Gel Supports and at High Pressure" Jetrahedron Letters. 38. 7583-7586 (1997)
[文献書誌] H.Kotsuki: "Organic Synthesis at High Pressure.Efficiet Ring Opening Reaction of Epoxides with Heterocydes" The Review of High Pressure Scionce and Technology. 7. (1998)
[文献書誌] M.Ciobanu: "Recent Advances in Organic Synthesis mder High Pressure" Liebigs Annalen. No.4. 623-635 (1997)
[文献書誌] K.Matsumoto: "Synthesis of Diazathia -15- and 18-crown Ethers and Their Tronspos Dropertios for Metal Cations" Heberocycles. 47(1). (1998)
[文献書誌] K.Matsumoto: "The Synthisis and Reactions of Heterocycles under High Pressures,Part II" Heberocycles. 47(2). (1998)
[文献書誌] A.Mori: "Diels-Alder Reaction of Fullerene C60 and 4-Hydroxytropones" Chomushy Letters. 395-396 (1997)
[文献書誌] A.Mori: "Dreparation of Tefrapheny lazulene quinodimerhanes from the Reactions of Azulenequirones with Dipherylketones and the IHNMR and UV-vis Specroal..." Chemisty Letters. 689-690 (1997)
[文献書誌] T.Asano: "Effects of Solvent Fluctuations on the Rate of the Tharmal 7/E Isonerization of N-Benmlidene arilines in a Highly Viscous Liquid Hydroxyanher" Bullertion of the Chemical Society of Japan. 70(1). 239-244 (1997)
[文献書誌] H.Sumi: "General Expression for Rates of Solution Reactions Influenced by Slow Solvent Fluctuations,and Its Experimental Evidence" Electrochimica Acta. 42(18). 2763-2777 (1997)
[文献書誌] T.Okuyama: "Vinylic SN2 Reaction of 1-Decenyliodonium Salt with Halide Ions" Balletin of the Chemical Sociehy of Japan. 71(1). 243-257 (1998)
[文献書誌] H.Tomioka: "Matrix Isolation Study of Reactive o-Quinoid Canpomds;Cenerasion,Detection and Reactions" Pure & Applied Chemistry. 837-840 (1997)
[文献書誌] H.Tomioka: "Polymerbylated and Poly(toA) butylated Dipherylcarbones,Genenation,Reactions,Kinetics,and Deuterium Isotope Effects of Slerically Cangested." Journal of the American Chemical Society. 119. 1582-1583 (1997)
[文献書誌] S.Murata: "Photochemical Reactionsof Meisitgl Azide with Tetacysnoethylene;Competibive Teopping of Singlet Nitrone and Didegydroazepines" Jouranal of Organic Chemisty. 62. 3055-3061 (1997)
[文献書誌] H.Tomioka: "Benzoxetene Direct Obseruation and Theoretical Studies" Chemisty Letters. 399-400 (1997)
[文献書誌] H.Tomioka: "Flash Flacuum Dyrolysis of Trifluoromethlated Dipheyldiazomethanes,Role of Trifluoronesyl Group on the Arylcarbone Rearrangenmert" Chemical Communications. 1745-1746 (1997)
[文献書誌] F.Morlet-Savary: "Ion and Radical Pair Gnosation in Tribronoacelophenone" Chemisty Letters. 1267-1268 (1997)
[文献書誌] H.Tomioka: "Persistent Triplet Carbones" Accounts of Chemical Research. 30. 315-321 (1997)
[文献書誌] B.Ohtani: "Role of Platirum Deponits on Titaniam(IV)Oxides Particles:Structural and Kinetic Aralyses of Photocetalytic Reaction in Aqueous Alcohol..." Journal of Physical Chemisty,B.101. 3349-3359 (1997)
[文献書誌] W.M.Dai: "Remarkable Tethering Effect on DNA Cleauage of Propargylic Suffone Corjugaties with Intercalatiy Moieties" Biomediciral Chemisty Letters. 8. 169-174 (1998)

1997 年度 実績報告書

極限反応場での物質変換新手法

研究代表者

小槻 日吉三 高知大学, 理学部, 助教授 (80093954)

研究成果

[文献書誌] H.Kotsuki: "A New Facile Method for the Chemoselective Roductive Transformafion of Azides to N-(tert-Batoxycarbonyl)amines" Jetrahedron Letlers. 38. 2129-2132 (1997)

[文献書誌] H.Kotsuki: "Yb(orf)_3-Catalyzed Michael Addition Reactions of β-Ketoesters on Silica Gel Supports and at High Pressure" Jetrahedron Letters. 38. 7583-7586 (1997)

[文献書誌] H.Kotsuki: "Organic Synthesis at High Pressure.Efficiet Ring Opening Reaction of Epoxides with Heterocydes" The Review of High Pressure Scionce and Technology. 7. (1998)

[文献書誌] M.Ciobanu: "Recent Advances in Organic Synthesis mder High Pressure" Liebigs Annalen. No.4. 623-635 (1997)

[文献書誌] K.Matsumoto: "Synthesis of Diazathia -15- and 18-crown Ethers and Their Tronspos Dropertios for Metal Cations" Heberocycles. 47(1). (1998)

[文献書誌] K.Matsumoto: "The Synthisis and Reactions of Heterocycles under High Pressures,Part II" Heberocycles. 47(2). (1998)

[文献書誌] A.Mori: "Diels-Alder Reaction of Fullerene C60 and 4-Hydroxytropones" Chomushy Letters. 395-396 (1997)

[文献書誌] A.Mori: "Dreparation of Tefrapheny lazulene quinodimerhanes from the Reactions of Azulenequirones with Dipherylketones and the IHNMR and UV-vis Specroal..." Chemisty Letters. 689-690 (1997)

[文献書誌] T.Asano: "Effects of Solvent Fluctuations on the Rate of the Tharmal 7/E Isonerization of N-Benmlidene arilines in a Highly Viscous Liquid Hydroxyanher" Bullertion of the Chemical Society of Japan. 70(1). 239-244 (1997)

[文献書誌] H.Sumi: "General Expression for Rates of Solution Reactions Influenced by Slow Solvent Fluctuations,and Its Experimental Evidence" Electrochimica Acta. 42(18). 2763-2777 (1997)

[文献書誌] T.Okuyama: "Vinylic SN2 Reaction of 1-Decenyliodonium Salt with Halide Ions" Balletin of the Chemical Sociehy of Japan. 71(1). 243-257 (1998)

[文献書誌] H.Tomioka: "Matrix Isolation Study of Reactive o-Quinoid Canpomds;Cenerasion,Detection and Reactions" Pure & Applied Chemistry. 837-840 (1997)

[文献書誌] H.Tomioka: "Polymerbylated and Poly(toA) butylated Dipherylcarbones,Genenation,Reactions,Kinetics,and Deuterium Isotope Effects of Slerically Cangested." Journal of the American Chemical Society. 119. 1582-1583 (1997)

[文献書誌] S.Murata: "Photochemical Reactionsof Meisitgl Azide with Tetacysnoethylene;Competibive Teopping of Singlet Nitrone and Didegydroazepines" Jouranal of Organic Chemisty. 62. 3055-3061 (1997)

[文献書誌] H.Tomioka: "Benzoxetene Direct Obseruation and Theoretical Studies" Chemisty Letters. 399-400 (1997)

[文献書誌] H.Tomioka: "Flash Flacuum Dyrolysis of Trifluoromethlated Dipheyldiazomethanes,Role of Trifluoronesyl Group on the Arylcarbone Rearrangenmert" Chemical Communications. 1745-1746 (1997)

[文献書誌] F.Morlet-Savary: "Ion and Radical Pair Gnosation in Tribronoacelophenone" Chemisty Letters. 1267-1268 (1997)

[文献書誌] H.Tomioka: "Persistent Triplet Carbones" Accounts of Chemical Research. 30. 315-321 (1997)

[文献書誌] B.Ohtani: "Role of Platirum Deponits on Titaniam(IV)Oxides Particles:Structural and Kinetic Aralyses of Photocetalytic Reaction in Aqueous Alcohol..." Journal of Physical Chemisty,B.101. 3349-3359 (1997)

[文献書誌] W.M.Dai: "Remarkable Tethering Effect on DNA Cleauage of Propargylic Suffone Corjugaties with Intercalatiy Moieties" Biomediciral Chemisty Letters. 8. 169-174 (1998)

1997 年度実績報告書

小槻日吉三高知大学, 理学部, 助教授 (80093954)