Developmental Research on Scale-up in Electrochemical Fluorination

电化学氟化放大技术的研究进展

• 批准号: 02555179
• 负责人: UNEYAMA Kenji
• 金额: $ 6.02万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02555179/
• 关键词: Fluorination; Electrooxidation; Trifluoromethylation; フッ素化; フッ素化合物; 電気化学; 有機電解合成; トリフルオロ

Developmental Research on Scale-up in Electrochemical FluorinationThis research consists of mainly two programs. The first is development of new electrochemical perfluoromethylation of olefins in a small sacle reactions and the second is a scale-up electrolysis of electrochemical trifluoromethylation, of methyl acrylate in 0. I kg scale by a flow cell electrolysis system.Electrochemical perfluoroalkylations of methyl acrylate, acrylamide, and acrylonitrile have been investigated. Perfluorooctanoic, butanoic, and difluoroacetic acids provided dimers of the corresponding perfluorinated carbon radicals in reasonable yields. In the oxygen atmosphere the electrolysis gave 2-oxo or. 2-hydroxy-4, 4, 4-trifluorobutylates in 30 - 45 % yields. This oxy-trifluoromethylation is promising for preparation of some valuable trifluoromethyl compounds otherwise difficult to prepare.A flow cell equipped with 10 X 10 cm^2 platinated titanium plates as electrodes was employed for 0. I Kg scale electrolysis of TFA and methylacrylate to give 50 % of the desired products at the current densities of 50 - 80 mA/cm^2. The temperature of the electrolysis affects current efficiency intensively. The lower temperature at around 0 C is desirable for the purpose.

电化学氟化放大的发展研究本研究主要包括两个项目。第一个是在小范围内开发新的电化学全氟甲基化烯烃反应，第二个是扩大电解电化学三氟甲基化，在0。1公斤秤由液流电池电解系统。研究了丙烯酸甲酯、丙烯酰胺和丙烯腈的电化学全氟烷基化反应。全氟辛酸、丁酸和二氟乙酸以合理的产量提供了相应的全氟碳自由基二聚体。在氧气环境中电解得到2-氧或。2-羟基- 4,4,4 -三氟丁酸盐收率为30 - 45%。这种氧-三氟甲基化很有希望制备一些有价值的三氟甲基化合物，否则很难制备。采用10 × 10 cm^2的镀钛板作为电极的液流池。在50 - 80 mA/cm^2的电流密度下，对TFA和甲基丙烯酸酯进行Kg级电解，得到所需产品的50%。电解温度对电流效率的影响很大。较低的温度在0℃左右是理想的。

项目成果

Kenji Uneyama,Masafumi Kobayashi: "Electrochemical Oxidation of N,N-Disubstituted Trifluoroacetamidic Acid;An Approach to N-Substituted 2-trifluoromethyl Benzimidaloes" J.Am.Chem.Soc.,.

Kenji Uneyama、Masafumi Kobayashi：“N,N-二取代三氟乙酰胺酸的电化学氧化；N-取代的 2-三氟甲基苯甲酰亚胺的方法”J.Am.Chem.Soc.,。

Kenji Uneyama: "Electrochemical Trifluoromethylation of Olefins ; Product-selectivity and Mechanistic Aspects" Tetrahedron. 45(4/5). 555-562 (1991)

Kenji Uneyama：“烯烃的电化学三氟甲基化；产物选择性和机理方面”四面体。

宇根山 健治: "Syntheses of 1-Aryl-2-trifluoromethylbenzimidazoles via Electrochemically Prepared P-Benzoquinone Imines" Tetrahedron Letters. 32. 5981-5982 (1991)

Kenji Uneyama：“通过电化学制备的对苯醌亚胺合成 1-芳基-2-三氟甲基苯并咪唑”Tetrahedron Letters 32. 5981-5982 (1991)

Kenji Uneyama: "Electrochemical Trifluoromethylation of Olefins;Product-selectivity and Mechanistic Aspects" Tetrahedron. 45. 555-562 (1991)

Kenji Uneyama：“烯烃的电化学三氟甲基化；产物选择性和机理方面”四面体。

Kenji Uneyama,Shunsuke Watanabe,Kouichi Kitagawa,Yukio Tokunaga,Yasuhiro Sato: "Perfluoroalkylation of Olefins by electrooxidation of Perfluoroalkanoic Acids;Relation between Product-selectivity and Current Density and Structure of Olefins" Bull.Chem.Soc.

Kenji Uneyama、Shunsuke Watanabe、Kouichi Kitakawa、Yukio Tokunaga、Yasuhiro Sato：“通过全氟链烷酸的电氧化实现烯烃的全氟烷基化；产物选择性与电流密度和烯烃结构之间的关系”Bull.Chem.Soc。