1996 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
応募区分	総合
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	近藤隆神戸大学, 医学部, 講師 (40143937) 片桐信弥東北大学, 薬学部, 助教授 (60089787) 富岡秀雄三重大学, 工学部, 教授 (20024599) 西本清一京都大学大学院, 工学研究科, 教授 (10115909) 安藤喬志滋賀医科大学, 医学部, 教授 (70029867)
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の活性化による分子認識能を有する超分子化合物、芳香族求核置換反応による芳香族アミン類の新規合成、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、エポキシ化合物と種々の求核試薬との高圧反応及びシリカゲルの添加効果、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化に配慮しつつ、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選択的分子変換。 3.フラッシュ気相熱分解(FVP): 中性2荷活性種の発生とこれの有機合成への応用、カルベン・ナイトレン等の高温気相下での反応、有機ケイ素・ゲルマニウム化合物の活性化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、高分子化合物の表面処理技術への適用、固体パーオキシラジカルの構造と反応性の解明。

研究成果

(40件)

すべてその他

すべて文献書誌 (40件)

[文献書誌] H.Kotsuki: "High Pressure Organic Chemistry.19. High Pressure Promoted,Silica Gel-Casalyzed Reaction of Epoxides with Nitrogen Heserocycles" Journal of Organic Chemistry. 61. 984-990 (1996)
[文献書誌] H.Kotsuki: "A Faule Conversion of Epoxides to β-Halohydrins with Silica Gel-Supported Lithium Halides" Tetrahedron Letters. 37. 1845-1848 (1996)
[文献書誌] H.Kotsuki: "Yttorbium(III) Trifluoromethanesulfonate Casalyzed High Pressure Reaction of Eporides with Indole. An Enantioselective Synthesis of (+)-Diolmycin AZ" Tetrahedron Letters. 37. 3727-3730 (1996)
[文献書誌] H.Kotsuki: "Synthesis of Novel Chiral Diazole Derivative Ligands for the Enantioselective Addition of Diethylzinc to Benzaldehyde" Journal of Organic Chemistry. 61. 8915-8920 (1996)
[文献書誌] 小槻日吉三: "超高圧条件下でのエポキシ開環反応" 化学工業. 47. 845-849 (1996)
[文献書誌] H.Kotsuki: "A New Faule Method for the Chemoselective Reductive Transformation of Azides to N-(tert-Butoxycarbonyl) amines" Tetrahedron Letters. 38(印刷中). (1997)
[文献書誌] T.Kimura: "Standardization of Ultrasonic Power of Sonochemical Reaction" Ultrasonics Sonochemistry. 3. S153-161 (1996)
[文献書誌] T.Ando: "Mechanism of Sonochemical Excitation in the Reactions of Lead Tetraacesate with Some Organic Substrates" Ultrasonics Sonochemistry. 3. S223-227 (1996)
[文献書誌] 安藤喬志: "ソノケミストリー-最近の動向と今後の展望" 化学工業. 47. 601-604 (1996)
[文献書誌] W.-M.Dai: "Synthesis of cis-Enediynes from 1,5-Diynes by Rearrangement of an Allylic Double Bond" Angew.Chem.,Int.Ed.Engl.35. 779-781 (1996)
[文献書誌] W.-M.Dai: "DNA Clearage of Novel Propargylic Sulfones. Enhancement of Potency via Intercalating Interaction" BioMed.Chem. Lett.6. 1093-1098 (1996)
[文献書誌] H.Tomioka: "Thermolysis and Photolysis of 1-Substituted Triptycenes. Divergent Pathways of Triptycyl Skeleton" J.Chem.Soc.,Perkin Trans.1. 563-569 (1996)
[文献書誌] N.Katagiri: "Deamination of 9-(hydroxymethylated cycloalkyl)-9H-adenines(carbocyclic ademine nucleosides) by adenosine deaminase : Effect of high pressure upon deamination rate and enan tioselectivity" Nucleosidas and Nucleotides. 15. 631-647 (1996)
[文献書誌] 片桐信弥: "酵素反応への高圧の適用" 化学工業. 47. 875-881 (1996)
[文献書誌] T.Kondo: "Sonolysis of ubiquinone in aqueous solutions. An EPR Spin trapping study" Int.J.Radiat.Biol.69(1). 113-121 (1996)
[文献書誌] T.Kondo: "Sonochemistry of cytochrome C.Evidence for superoxide formation by ultrasound in argon-saturated aqueous solution" Ultrasonics Sonochemistry. 3. S193-200 (1996)
[文献書誌] 近藤隆: "生体への超音波照射の影響" 化学工業. 47(8). 631-637 (1996)
[文献書誌] K.Matsumoto: "High Pressure Diels-Alder Reactions of Pyridone with Cyclooctyne" Heterocycles. 45. 15-18 (1997)
[文献書誌] 林直人: "超高圧を利用する有機化学-現状と今後の展開-" 化学工業. 47. 833-836 (1996)
[文献書誌] K.Kuzuya: "Effect of Alkyl Substituent on Plasma-Induced Free Radicals of Cellulose Derivatives" Proc.Jpn.Symp.Plasma Chem.9. 55-60 (1996)
[文献書誌] M.Kuzuya: "Special Features of Peroxy Rodicals on Plasma Inadiated Polymers" J.Photopolym.Sci.Technol.9. 261-264 (1996)
[文献書誌] M.Kuzuya: "A Novel Collision-Induced Solid State Radical Recombination" Mol.Cryst.Liq.Ctyst.277. 343-349 (1996)
[文献書誌] M.Tezuka: "Oxidation of Aromatic Hydrocarbons with Oxygen in a Radiofrequency Plasma" Plasma Chem.Plasma Process.16. 329-340 (1996)
[文献書誌] M.Tezuka: "Plasma Chemistry for Development of Novel Materials" Chemical Sciences. (印刷中).
[文献書誌] F.Toda,H.Liu,I.Miyahara and K.Hirotsu: "Design of new host compounds,1,1-bis(diarylhydroxymethyl) ferrocenes" J.Chem.Soc.,Perkin Trans.2. 85-88 (1997)
[文献書誌] F.Toda,H.Miyamoto,S.Kikuchi,R.Kuroda and F.Nagami: "Enantioselective Photocyclization of 2-Arylthio-3-methylcyclohexen-1-ones to Dihydrobenzothiophene Derivatives in an Inclusion Crystal with an Optically Active Host" J.Am.Chem.Soc.118. 11315-11316 (1996)
[文献書誌] G.Kaupp,J.Schmeyers,F.Toda,H.Takumi and H.Koshima: "Mechanism of Solid-Solid Resolution of Pantolactone" J.Phys.Org.Chem.9. 795-800 (1996)
[文献書誌] M.R.Caira,A.Coetzee,L.R.Nassimbeni and F.Toda: "Inclusion of Dioxolane by a Tricyclic Diol Host : Structure and Kinetics" J.Chem.Research(s). 280-281 (1996)
[文献書誌] F.Toda and M.Ochi: "Enantioselective Oxidation of Imines in Inclusion Complex with a Chiral Host Compound and Preparation of Optically Pure Oxaziridines by Enantiomer Resolution" Enantiomer. 1. 85-88 (1996)
[文献書誌] S.A.Bourne,K.L.Gifford Nash and F.Toda: "Inclusion compounds with a sexipedal host. Ctystal sturctures and thermal analysis of inclusion compounds of hexakis(3-hydroxy-3,3-diphenylprop-2-ynyl) benzene with methyl ethyl ketone,diethyl ketone and diethyl ether" J.Chem.Soc.,Perkin Trans.2. 2145-2149 (1996)
[文献書誌] R.Cimiraglia: "Mechanism of Thermal Z/E Isomerization of Aromatic Azo Compounds,Relation between Rotation and Inversion States" Gazetla Chimica Italiana. 126(10). 679-683 (1996)
[文献書誌] 浅野努: "高圧下のZ/E異性化反応" 化学工業. 47(11). 882-888 (1996)
[文献書誌] T.Asano: "Effects of Solvent Fluctuations on the Rate of the Thermal Z/E Isomerization of N-Benzylideneanilines in Highly Viscous Liquid Hydrocarbon" Bulletin 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" Electrochim.Acta. 印刷中.
[文献書誌] K.Matsumoto: "Molecular Inclusion Crystals of Novel Heterocyclic Host Compounds" Mol.Cryst.Liq.Cryst.276. 173-184 (1996)
[文献書誌] T.Kondo: "Radiation Research 1895-1995,Vol.2 Congress Lectures" Universitatsdruckerei H.Sturtz AG, 4 (1996)
[文献書誌] K.Ikeda: "Hyperthermic Oncology in Japan '96" Fukuoka Printing Co., 2 (1996)
[文献書誌] 近藤隆: "磁気共鳴と医学" 日本医学館, 4 (1996)
[文献書誌] Fumio Toda: "Comprehensive Supramolecular Chemistry : Volume 6,Solid-State Supramolecular Chemistry : Crystal Engineering,"Diol,Bisphenol,and Diamide Host Compounds"" Pergamon, 966 (1996)
[文献書誌] K.Tanaka and F.Toda: "Comprehensive Supramolecular Chemistry : Volume 6,Solid-State Supramolecular Chemistry : Crystal Engineering,"Onium Salt Hosts"" Pergamon, 966 (1996)

1996 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: "High Pressure Organic Chemistry.19. High Pressure Promoted,Silica Gel-Casalyzed Reaction of Epoxides with Nitrogen Heserocycles" Journal of Organic Chemistry. 61. 984-990 (1996)

[文献書誌] H.Kotsuki: "A Faule Conversion of Epoxides to β-Halohydrins with Silica Gel-Supported Lithium Halides" Tetrahedron Letters. 37. 1845-1848 (1996)

[文献書誌] H.Kotsuki: "Yttorbium(III) Trifluoromethanesulfonate Casalyzed High Pressure Reaction of Eporides with Indole. An Enantioselective Synthesis of (+)-Diolmycin AZ" Tetrahedron Letters. 37. 3727-3730 (1996)

[文献書誌] H.Kotsuki: "Synthesis of Novel Chiral Diazole Derivative Ligands for the Enantioselective Addition of Diethylzinc to Benzaldehyde" Journal of Organic Chemistry. 61. 8915-8920 (1996)

[文献書誌] 小槻日吉三: "超高圧条件下でのエポキシ開環反応" 化学工業. 47. 845-849 (1996)

[文献書誌] H.Kotsuki: "A New Faule Method for the Chemoselective Reductive Transformation of Azides to N-(tert-Butoxycarbonyl) amines" Tetrahedron Letters. 38(印刷中). (1997)

[文献書誌] T.Kimura: "Standardization of Ultrasonic Power of Sonochemical Reaction" Ultrasonics Sonochemistry. 3. S153-161 (1996)

[文献書誌] T.Ando: "Mechanism of Sonochemical Excitation in the Reactions of Lead Tetraacesate with Some Organic Substrates" Ultrasonics Sonochemistry. 3. S223-227 (1996)

[文献書誌] 安藤喬志: "ソノケミストリー-最近の動向と今後の展望" 化学工業. 47. 601-604 (1996)

[文献書誌] W.-M.Dai: "Synthesis of cis-Enediynes from 1,5-Diynes by Rearrangement of an Allylic Double Bond" Angew.Chem.,Int.Ed.Engl.35. 779-781 (1996)

[文献書誌] W.-M.Dai: "DNA Clearage of Novel Propargylic Sulfones. Enhancement of Potency via Intercalating Interaction" BioMed.Chem. Lett.6. 1093-1098 (1996)

[文献書誌] H.Tomioka: "Thermolysis and Photolysis of 1-Substituted Triptycenes. Divergent Pathways of Triptycyl Skeleton" J.Chem.Soc.,Perkin Trans.1. 563-569 (1996)

[文献書誌] N.Katagiri: "Deamination of 9-(hydroxymethylated cycloalkyl)-9H-adenines(carbocyclic ademine nucleosides) by adenosine deaminase : Effect of high pressure upon deamination rate and enan tioselectivity" Nucleosidas and Nucleotides. 15. 631-647 (1996)

[文献書誌] 片桐信弥: "酵素反応への高圧の適用" 化学工業. 47. 875-881 (1996)

[文献書誌] T.Kondo: "Sonolysis of ubiquinone in aqueous solutions. An EPR Spin trapping study" Int.J.Radiat.Biol.69(1). 113-121 (1996)

[文献書誌] T.Kondo: "Sonochemistry of cytochrome C.Evidence for superoxide formation by ultrasound in argon-saturated aqueous solution" Ultrasonics Sonochemistry. 3. S193-200 (1996)

[文献書誌] 近藤隆: "生体への超音波照射の影響" 化学工業. 47(8). 631-637 (1996)

[文献書誌] K.Matsumoto: "High Pressure Diels-Alder Reactions of Pyridone with Cyclooctyne" Heterocycles. 45. 15-18 (1997)

[文献書誌] 林直人: "超高圧を利用する有機化学-現状と今後の展開-" 化学工業. 47. 833-836 (1996)

[文献書誌] K.Kuzuya: "Effect of Alkyl Substituent on Plasma-Induced Free Radicals of Cellulose Derivatives" Proc.Jpn.Symp.Plasma Chem.9. 55-60 (1996)

[文献書誌] M.Kuzuya: "Special Features of Peroxy Rodicals on Plasma Inadiated Polymers" J.Photopolym.Sci.Technol.9. 261-264 (1996)

[文献書誌] M.Kuzuya: "A Novel Collision-Induced Solid State Radical Recombination" Mol.Cryst.Liq.Ctyst.277. 343-349 (1996)

[文献書誌] M.Tezuka: "Oxidation of Aromatic Hydrocarbons with Oxygen in a Radiofrequency Plasma" Plasma Chem.Plasma Process.16. 329-340 (1996)

[文献書誌] M.Tezuka: "Plasma Chemistry for Development of Novel Materials" Chemical Sciences. (印刷中).

[文献書誌] F.Toda,H.Liu,I.Miyahara and K.Hirotsu: "Design of new host compounds,1,1-bis(diarylhydroxymethyl) ferrocenes" J.Chem.Soc.,Perkin Trans.2. 85-88 (1997)

[文献書誌] F.Toda,H.Miyamoto,S.Kikuchi,R.Kuroda and F.Nagami: "Enantioselective Photocyclization of 2-Arylthio-3-methylcyclohexen-1-ones to Dihydrobenzothiophene Derivatives in an Inclusion Crystal with an Optically Active Host" J.Am.Chem.Soc.118. 11315-11316 (1996)

[文献書誌] G.Kaupp,J.Schmeyers,F.Toda,H.Takumi and H.Koshima: "Mechanism of Solid-Solid Resolution of Pantolactone" J.Phys.Org.Chem.9. 795-800 (1996)

[文献書誌] M.R.Caira,A.Coetzee,L.R.Nassimbeni and F.Toda: "Inclusion of Dioxolane by a Tricyclic Diol Host : Structure and Kinetics" J.Chem.Research(s). 280-281 (1996)

[文献書誌] F.Toda and M.Ochi: "Enantioselective Oxidation of Imines in Inclusion Complex with a Chiral Host Compound and Preparation of Optically Pure Oxaziridines by Enantiomer Resolution" Enantiomer. 1. 85-88 (1996)

[文献書誌] R.Cimiraglia: "Mechanism of Thermal Z/E Isomerization of Aromatic Azo Compounds,Relation between Rotation and Inversion States" Gazetla Chimica Italiana. 126(10). 679-683 (1996)

[文献書誌] 浅野努: "高圧下のZ/E異性化反応" 化学工業. 47(11). 882-888 (1996)

[文献書誌] T.Asano: "Effects of Solvent Fluctuations on the Rate of the Thermal Z/E Isomerization of N-Benzylideneanilines in Highly Viscous Liquid Hydrocarbon" Bulletin 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" Electrochim.Acta. 印刷中.

[文献書誌] K.Matsumoto: "Molecular Inclusion Crystals of Novel Heterocyclic Host Compounds" Mol.Cryst.Liq.Cryst.276. 173-184 (1996)

[文献書誌] T.Kondo: "Radiation Research 1895-1995,Vol.2 Congress Lectures" Universitatsdruckerei H.Sturtz AG, 4 (1996)

[文献書誌] K.Ikeda: "Hyperthermic Oncology in Japan '96" Fukuoka Printing Co., 2 (1996)

[文献書誌] 近藤隆: "磁気共鳴と医学" 日本医学館, 4 (1996)

[文献書誌] Fumio Toda: "Comprehensive Supramolecular Chemistry : Volume 6,Solid-State Supramolecular Chemistry : Crystal Engineering,"Diol,Bisphenol,and Diamide Host Compounds"" Pergamon, 966 (1996)

[文献書誌] K.Tanaka and F.Toda: "Comprehensive Supramolecular Chemistry : Volume 6,Solid-State Supramolecular Chemistry : Crystal Engineering,"Onium Salt Hosts"" Pergamon, 966 (1996)

1996 年度実績報告書

小槻日吉三高知大学, 理学部, 助教授 (80093954)