The Application Of Electrochemical Fluorination Of Chlorinated Diisopropyl Phosphine And Imidazole And Fluorinated Products

Fluorin is the most vivacious,and the strongest electronegative of all nonmatal elements.When fluorin is imported into organic compounds,their chemical and physical properties can be significantly changed.The pharmaceutical has series of special properties such as mimesis effect,lipophilic effect and stability etc.,which result in less toxicity,better metabolizability,longer pharmic effect and higher curative effect,when fluorin element or groups containing fluorin are imported into pharmaceutical.Although many methods of preparation of fluoroorganics have been developed to date,they often have unavoidable didadvantages such as complicated equipment,toxic reagents,hazardous operation,serious pollution,and multistep routs in chemical fluorination.Electrochemical fluorination,as a novel fluorination method,can import fluorin into organic compounds directly under mild conditions. Electrochemical fluorination can be classified into two sorts:perfluorination and selective fluorination.Electrochemical fluorination of Chlorodiisopropylphosphine and imidazole,and the product of fluorinated Chlorodiisopropylphosphine as electrolyte of Lithium ion secondary batteries were studied in the paper.The paper is comprised of three parts.The first part:Isopropylmagnesium Chloride is provided by the reaction of Magnesium and Isopropyl chlorides.Then Isopropylmagnesium Chloride and Phosphorus Trichloride make Chlorodiisopropylphosphine.The optimal reaction conditions are as follows: -30℃～-35℃,1.25 hour,PCl₃:i-C₃H₇Cl=1:1.8.The reactor was irradiated in the ultrasound.The yield was increased to 80.1%.Triethylamine tris(hydrogen fluoride) is synthesized,using triethylamine and anhydrous hydrogen fluoride as starting materials and carbon tetrachloride as the solvent.The optimal reaction conditions are as follows:0～5℃,dripping triethylamine and tetrachloride carbon solution toAHF under mix round.The second part:Under the conditions that the temperature is about 0～-5℃,the cell voltage is 4.7～5.3V,the current density is 0.15～0.35A·dm^-2,nickel as anode, stainless steel as cathode.Preparation of Fluorinated Alkylphosphorane is carried out by utilizing the typical tubby electrobath.Under the conditions that the temperature is about 10～20℃,the cell voltage is 1.1～1.3V,the current density is 0.20～0.35A·dm^-2,carbon as anode and cathode.Preparation of Fluorinated imidazole is carried out by utilizing the only one room vitreous electrobath.The third part:Fluorinated Alkylphosphoranes are reacted with LiF in organic solvent of EC and DME This solution can be used directly as electrolyte after filtering.Study on the chemical and electrochemical characters about the electrolyte.The electrolyte was studied by a secondary cell testing system.Using LiCoO₂ as anode,Li as cathode,it was found that the discharge platform was3.7V,initial discharge capacity was 107mA·h·g^-1 and efficiency still remained 102%after cycled 50 timeswhile capacity decreased largely after 40 times.The electrochemical impedance spectroscopy diagram showedthat the electrolyte electrochemical impedance was nearly 140Ω.The results indicated that the lithium perfluoroalkylphosphonate was expected to be the new electrolyte salt of lithiumion rechargeable batteries.