An environmentally benign electrochemical trifluoromethylation of methyl isonicotinate by cyclic voltammetry and galvanostatic electrolysis
摘要
Trifluoromethylation reactions elicited a lot of attention because they are used to produce fluorinated compounds, which are extremely important in medicinal chemistry. The CF3 group has exemplary properties such as high electron density, lipophilicity, enhanced acidity, and metabolic stability, and CF3 substituted compounds play essential roles in medicines, agrochemicals, and materials research. This paper describes a successful electrochemical trifluoromethylation of Methyl Isonicotinate (MIN) using trifluoroacetic acid as the CF3 donor and triethylamine, pyridine and sodium trifluoroacetate as redox mediators in an acetonitrile medium at platinum and glassy carbon electrodes using cyclic voltammetry. The approach is simple, eco-friendly, and pre-functionalization is not required. Linear sweep voltammetry indicates that MIN does not have a discrete oxidation peak of 0.016 V vs. Ag, and the oxidation within the gas evolution region. TFA/NaTFA exhibits a little greater current density in the oxidation of MIN than in the other media. The adsorption of MIN/products on the glassy carbon electrode is indicated by broad anodic peaks in cyclic voltammetry. Galvanostatic electrolysis reveals that TFA/TEA/ACN gives superior conversion whereas TFA/NaTFA gives very low conversion (3%).
Graphical Abstract