Basic Study on Solvent Free Organic Electrosynthesis

无溶剂有机电合成基础研究

• 批准号: 13650914
• 负责人: FUCHIGAMI Toshio
• 金额: $ 2.18万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650914/
• 关键词: Green Chemistry; lonic liquide; Room temperature molten salts; Polythiophene; Polypyrrole; Electropolymerization; Conducting polymer in Electrochemical fluorination; イオン性液体; イミダゾール塩; キャパンタ; 常温溶媒塩; フッ素化エーテル; フッ素化ラクトン; フッ素化環状カーボナート; フッ素化フタリド

Solvent free electroorganic synthesis is highly desirable from an enviromental aspect. In this project, we have achieved the following subjects.1) Hardly oxidizable cyclic carbonates and lactones were anodically fluorinated in Et_4NF・4HF without any solvents with execellent current efficiencies. Biologically interesting phthalides were also successfully fluorinated only in a mixture of imidazolium molten salts and Et_4NF・nHF (n=4,5).2) Conducting polymers were prepared by anodic oxidation of pyrrole and thiophene in room temperature molten salts like 1-ethyl-3-methy limidazolium trifloromethanesulfonate. The morphological stuructures of polypyrrole and polythiophene prepared in the room temperature molten salts are quite different from those obtatined in organic solvents and water. The electrochemical capacity and electroconductivity were greatly increased.3) We have demonstrated the reuse of room temperature molten salts for organic electrosynthesis.Thus, we have achieved solvent free organic etectrosynthesis and the results seem to be useful for future study on solvent free organic electrode processes.

无溶剂有机电合成是一种环境友好的合成方法。本课题主要完成了以下几个方面的工作：1）在无溶剂的Et_4NF·4 HF溶液中，以极高的电流效率对难氧化的环状碳酸酯和内酯进行了阳极氟化。在咪唑盐和Et_4NF·nHF（n= 4，5）的混合溶液中，也成功地氟化了具有生物学意义的苯酞类化合物。2）在1-乙基-3-甲基咪唑三氟甲磺酸盐等室温熔盐中，通过阳极氧化吡咯和噻吩制备导电聚合物。在室温熔盐中制备的聚吡咯和聚噻吩的形态结构与在有机溶剂和水中制备的有很大的不同。电化学容量和电导率大大提高。3）我们证明了室温熔盐在有机电合成中的重复使用，从而实现了无溶剂有机电合成，这一结果对未来无溶剂有机电极过程的研究具有重要意义。

项目成果

Masaru Hasegawa: "Selective Anodic Fluorination of Phthalides in Ionic Liquids"Green Chemistry. (印刷中).

长谷川胜：“离子液体中邻苯二甲酸盐的选择性阳极氟化”绿色化学（出版中）。

HASEGAWA MASARU: "HIGHLY REGIOSELECTIVE ANODIC MONOFLUORINHTION OF GAIC ETHERS, LACTONES, AND A Cyclic CARBONATE"TETRAHEDRON LETTERS. 43・8. 1503-1505 (2002)

长谷川胜：“GAIC 醚、内酯和环状碳酸酯的高度区域选择性阳极单氟化”四面体字母 43・8 (2002)。

MASARU HASEGAWA: "ELECTROORGANIC SYNTHESIS UNDER SOLVENT-FREE CONDITIONS"TETRAHEDRON LETTERS. 43(印刷中). (2002)

MASARU HASEGAWA：“无溶剂条件下的有机电合成”Tetrahedron Letters 43（印刷中）。

Masaru Hasegawa: "Electroorganic Synthesis under Solvent Free Conditions"Tetrahedron Letters. 43. 1505-1507 (2002)

长谷川胜：《无溶剂条件下的有机电合成》四面体快报。

Rei Sekiguchi: "Electrooxidative polymerization of Aromatic Compounds in Room Temperature Ionic Liquid"J. Electroanal. Chem.. (印刷中).

Rei Sekiguchi：“室温离子液体中芳香族化合物的电氧化聚合”J. Electroanal。