1995 Fiscal Year Annual Research Report

極限反応場での物質変換新手法

Research Project

Project/Area Number	07304047
Research Category	Grant-in-Aid for Co-operative Research (A)
Research Institution	Kochi University
Principal Investigator	小槻日吉三高知大学, 理学部, 助教授 (80093954)
Co-Investigator(Kenkyū-buntansha)	富岡秀雄三重大学, 工学部, 教授 (20024599) 中村栄一東京大学, 大学院・理学系研究科, 教授 (00134809) 安藤高志滋賀医科大学, 医学部, 教授 (70029867) 森章九州大学, 機能物質科学研究所, 助教授 (70038602) 井畑敏一大阪大学, 理学部, 教授 (80029644)
Keywords	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
Research Abstract	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新機能性有機化合物・イオノフォア等の合成、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反応の促進、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反応における無触媒化あるいはシリカゲルの添加効果、さらにはいくつかの新規反応の開発。 2 超音波環境下の有機合成: 超音波照射条件で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、ラジカルの空気酸化、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有機固相状態での選択的分子移動。 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・ニ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と有機ヘテロ原子化合物の合成、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。

Research Products
(14 results)

All Other

All Publications (14 results)

[Publications] H. Kotsuki: "Synthesis of Novel Chiral Diazole Ligands for Enantioselective Addition of Diethylzine to Benzaldehyde" Tetrahedron : Asymmetry. 6. 2665-2668 (1995)
[Publications] H. Kotsuki: "High Pressure Organic Chemistry 19 High Pressure Promoted, Silica Gel-Catalyzed Reaction of Epoxides with Nitrogen Heterocycles" Journal of Organic Chemistry. 61. 484-990 (1996)
[Publications] H. Kotsuki: "A New Faule Conversion of Epoxides to β-Halohydrins with Silica Gel-Supported Lithium Halides" Tetrahedron Letters. 37(印刷中). (1996)
[Publications] T. Ibata: "Reaction of Mono-,Di-,and Trichloronitrobenzenes with N-Methyl Substituted Cyclic Tertiary Amines under High Pressure" Bulletin of the Chemical Society of Japan. 68. 2717-2726 (1995)
[Publications] T. Ibata: "The Nucleophilic Substitution Reaction of p-Chloronitrobenzenes with N-Substituted Cyclic Amines under High Pressure" Bulletin of the Chemical Society of Japan. 68. 2941-2949 (1995)
[Publications] T. Ibata: "The SNAr Reaction of 2,3,5,6-Tetrachloronitrobenzene with Diamines under High Pressure : Formation of Cyclization Products" Bulletin of the Chemical Society of Japan. 68. 3227-3232 (1995)
[Publications] T. Nozoe: "Diels-Alder Reactions of 3-Bromo-1,5-azulene quirone and 3-Bromo-1,7-azulene quinone with Several Dienophiles High Pressure Acceleration" Synlett. 375-377 (1995)
[Publications] H. Takeshita: "Highly Thermally-Stable Diels-Alder Adducts of [60] Fullerene with Z-Cycloalkenones and Their Acetals" Chemistry Letters. 377-378 (1995)
[Publications] H. Takeshita: "High-Pressue Diels-Alder Reaction of Cyclooctateteaene with Dimethyl 1,4-Dimethyl-7-oxabicyclo [2,2,1] hepta-2,5-diene-2,3-dioate, Single Crystalline ・・・・" Bulletin of the Chemical Society of Japan. 68. 2669-2677 (1995)
[Publications] T. Kimura: "The Site of Sonochemically-Initialed Radical Reaction of Lead Tetraacetate with β-Methylstyrone" Chemistry Letkrs. 55-56 (1995)
[Publications] T. Kimura: "Isomerization Mechanism of α-Phenetlyl Thiocyanate in the Dresence of a Supported Reasont" Bulletin of Shiga University of Medical Science. 6. 1-5 (1995)
[Publications] T. Ando: "Mechanism of Sonochemical Excitation in the Reactions of Lead Tetra-acetate with Some Organic Substrates" Ultrasonics Sonochemistry. 3(印刷中). (1996)
[Publications] E. Nakamura: "Sonochemical Synthesis of Alkyl Hydropes oxide by Aerobic Roductive Oxygeneation of Allcyl Halide" Synlett. 525-526 (1995)
[Publications] H. Tomioka: "Triptycyl (aryl) carbenes A Romarkably Effective Kinetic Stabilizer of Triplet Carbenes" Journal of the American Chemical Society. 117. 11355-11356 (1995)

1995 Fiscal Year Annual Research Report

極限反応場での物質変換新手法

Principal Investigator

小槻 日吉三 高知大学, 理学部, 助教授 (80093954)

Research Products

[Publications] H. Kotsuki: "Synthesis of Novel Chiral Diazole Ligands for Enantioselective Addition of Diethylzine to Benzaldehyde" Tetrahedron : Asymmetry. 6. 2665-2668 (1995)

[Publications] H. Kotsuki: "High Pressure Organic Chemistry 19 High Pressure Promoted, Silica Gel-Catalyzed Reaction of Epoxides with Nitrogen Heterocycles" Journal of Organic Chemistry. 61. 484-990 (1996)

[Publications] H. Kotsuki: "A New Faule Conversion of Epoxides to β-Halohydrins with Silica Gel-Supported Lithium Halides" Tetrahedron Letters. 37(印刷中). (1996)

[Publications] T. Ibata: "Reaction of Mono-,Di-,and Trichloronitrobenzenes with N-Methyl Substituted Cyclic Tertiary Amines under High Pressure" Bulletin of the Chemical Society of Japan. 68. 2717-2726 (1995)

[Publications] T. Ibata: "The Nucleophilic Substitution Reaction of p-Chloronitrobenzenes with N-Substituted Cyclic Amines under High Pressure" Bulletin of the Chemical Society of Japan. 68. 2941-2949 (1995)

[Publications] T. Ibata: "The SNAr Reaction of 2,3,5,6-Tetrachloronitrobenzene with Diamines under High Pressure : Formation of Cyclization Products" Bulletin of the Chemical Society of Japan. 68. 3227-3232 (1995)

[Publications] T. Nozoe: "Diels-Alder Reactions of 3-Bromo-1,5-azulene quirone and 3-Bromo-1,7-azulene quinone with Several Dienophiles High Pressure Acceleration" Synlett. 375-377 (1995)

[Publications] H. Takeshita: "Highly Thermally-Stable Diels-Alder Adducts of [60] Fullerene with Z-Cycloalkenones and Their Acetals" Chemistry Letters. 377-378 (1995)

[Publications] H. Takeshita: "High-Pressue Diels-Alder Reaction of Cyclooctateteaene with Dimethyl 1,4-Dimethyl-7-oxabicyclo [2,2,1] hepta-2,5-diene-2,3-dioate, Single Crystalline ・・・・" Bulletin of the Chemical Society of Japan. 68. 2669-2677 (1995)

[Publications] T. Kimura: "The Site of Sonochemically-Initialed Radical Reaction of Lead Tetraacetate with β-Methylstyrone" Chemistry Letkrs. 55-56 (1995)

[Publications] T. Kimura: "Isomerization Mechanism of α-Phenetlyl Thiocyanate in the Dresence of a Supported Reasont" Bulletin of Shiga University of Medical Science. 6. 1-5 (1995)

[Publications] T. Ando: "Mechanism of Sonochemical Excitation in the Reactions of Lead Tetra-acetate with Some Organic Substrates" Ultrasonics Sonochemistry. 3(印刷中). (1996)

[Publications] E. Nakamura: "Sonochemical Synthesis of Alkyl Hydropes oxide by Aerobic Roductive Oxygeneation of Allcyl Halide" Synlett. 525-526 (1995)

[Publications] H. Tomioka: "Triptycyl (aryl) carbenes A Romarkably Effective Kinetic Stabilizer of Triplet Carbenes" Journal of the American Chemical Society. 117. 11355-11356 (1995)

小槻日吉三高知大学, 理学部, 助教授 (80093954)