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Preparation and Reaction of Trifluoromethy-Metal Complexes

三氟甲基金属配合物的制备与反应

基本信息

批准号：
01550675
负责人：
UNEYAMA Kenji
金额：
$ 1.09万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01550675/
关键词：
Trifluoromethylation Fluorine Compound Fluorination Electrolysis 2フッ化キセノン

项目摘要

1. Trifluoromethylation by Electron-Transfer Reaction from Chalocogenides to Trifluoromethyl Bromide.Reaction of trifluoromethyl bromide (CF_3Br) with chlalcogenides (Ar-X^-, X ; S, Se, Te) proceeds smoothly, generating CF_3・radicals which are trapped with Olefins. Thus, 1, 2-addition of CF_3 and Ar-X units to carboncarbon bond was performed. One electron transfer from ArX^- to CF_3Br was proposed where the order of the reactivity of ArX^- is as follows ArTe > ArSe > ArS. Particularly, arene telluride reacts even at -40^ﾟC. Electron-rich olefins are more reactive so that vinyl ethers give a reasonable yield of 1, 2-addition products. Reaction of arene thiolate is slower than that of the corresponding selenide. However, a small amaunt of selenide catalyzes the trifluoromethyl-sulfenylation. This result suggests that arene-selenide mediated trifluoromethgl-alkylation and the related 1, 2-addition would be possible.2. Electrochemical TrifluoromethylationElectrochemical oxidation of trifluoroacetic acid in the presence of butyl acrylate under oxygen atmosphere provides trifluoromethylated -oxo of -hydroxy carboxylate in 45% yield. The trifluoro-methylated carbon radicals are trapped with molecular oxygen leading to the desired carboxylate. Content of water in methanol affected the yield of the oxygenated compounds presumably because water is electro-oxidized in the same conditions of TFA oxidation.

1.氯属化合物的电子转移反应生成三氟甲基溴三氟甲基溴（CF_3Br）与氯属化合物（Ar-X^-，X ; S，Se，Te）的反应顺利进行，生成CF_3·自由基，这些自由基被烯烃捕获。从而实现了CF_3和Ar-X单元在碳碳键上的1，2-加成。提出了ArX^-到CF_3Br的单电子转移，其中ArX^-的反应活性顺序为ArTe > ArSe > ArS。特别地，芳烃碲化物甚至在-40 ° C下反应。富电子烯烃的反应性更强，因此乙烯基醚得到合理的1，2-加成产物产率。芳烃硫醇盐的反应比相应的硒化物慢。然而，少量硒化物催化三氟甲基亚磺酰化。这一结果表明，芳烃硒化物介导的三氟甲基烷基化反应及相关的1，2-加成反应是可能的.电化学三氟甲基化在丙烯酸丁酯存在下，在氧气气氛下，三氟乙酸的电化学氧化以45%的产率提供-羟基羧酸的三氟甲基氧代。三氟甲基化的碳自由基被分子氧捕获，得到所需的羧酸盐。甲醇中的水含量影响含氧化合物的产率，这可能是因为水在TFA氧化的相同条件下被电氧化。