电化学2017，Vol.23Issue(3)：316-321,6.DOI:10.13208/j.electrochem.161043
甲基磺酰氟Simons电化学氟化过程特性和机理研究
Characteristics and Mechanism for the Simons Electrochemical Fluorination of Methanesulfonyl Fluoride
摘要
Abstract
The characteristics and mechanism for the Simons electrochemical fluorination processes were investigated during the electrochemical fluorination of CH3SO2F to CF3SO2F.The results showed that the reaction mechanism for the electrochemical fluorination of organic compounds to organic fluorides was the same as that of chemical fluorination processes using fluorinating agents such as CoF3.The electrochemical fluorination in anhydrous HF was a heterogeneous process,and nickel fluorides on the surface of the nickel anode played the role of a mediator in the Simons process to transfer oxidation potential from the anode to the substrate and fluorine from HF to the organic substance.Nickel fluorides were formed electrochemically on the surface of the nickel anode by oxidation of Ni in anhydrous HF to a high valence (with the oxidation stage more than +2) nickel fluorides.The fluorinat ing agents in electrochemical fluorination processes were NiFn(n ≥3),high valences of nickel produced at the anode,which is much more reactivie than CoF3 and instable under the experimental conditions.The decomposion of NiFn to F2 would take place,and NiFn could also react with organic fluoride.Because F2 is a strong fluorinating agent,NiFn could be decomposed into low molecular weight organic compounds fluorinated products,leading to low current efficiency in process yield and by-products.Therefore,an effective method to improve the process is by increasing the molar ration of organic matter to NiFn on the anode/electrolyte interface.关键词
Simons电化学氟化/CH3SO2F/氟化过程机理Key words
Simons electrochemical fluorination/CH3SO2F/reaction mechanism分类
化学化工引用本文复制引用
许文林,李宝同,王大为,王雅琼..甲基磺酰氟Simons电化学氟化过程特性和机理研究[J].电化学,2017,23(3):316-321,6.基金项目
国家自然科学基金项目(No.21076173)资助 （No.21076173）
