Preparation Of Tempo-IL/Polymeric Ionic-liquid/Carbon Black Ternary Composite And Its Application In Electrochemical Oxidation

Electroorganic chemistry,as a green chemistry synthesis method,provides a benign and practical approach to synthesis,and has received increasing attention.Electrochemical synthesis also has some problems.Unfortunately,some applications necessitate the use of large amounts of supporting electrolyte to ensure ionic conductivity and the efficient movement of charge.As a result,one can be faced with a tedious workup and the waste of resources.Therefore,the study about the recycle of the supporting electrolyte and elector-catalyst are valuable.Our partner,the Little group from UCSB,developed a recyclable composite by a polymeric ionic liquid(PIL)and carbon nanoparticle composite featuring conductive Super P? carbon black(CB).Then the recyclable composite was used as the supporting electrolyte and a series of electrochemical test was applied,it was found that it has highly electrochemical stability characters and widely electrochemical window,what's more,it can be recycle just by simple process.On the basis of above study,we conducted the further research:(1)Ionic-liquid TEMPO-IL-BF4 was firstly synthesized from 4–hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.The reaction of poly dimethyldiallylammonium chloride(PDDA)and bis(trifluoromethane)sulfonimide lithium salt(LiTFSI)gave poly[diallyldimethylammonium bis(trifluoromethanesulfonyl)imide](PDDA(Tf2N).The combination of the two synthesized materials and carbon black afforded ternary composite,which was used as recoverable supporting electrolyte and mediator for the electrochemical oxidation of alcohol.The results indicates that various alcohol can be oxidized efficiently to the corresponding aldehydes or ketones in more than 80% yields in the presence of the ternary composite under electrochemical conditions.In addition,the composite can be recovered,with 95% yield after 4 experiments.(2)The electrochemical oxidative functionalization of tetrahydroisoquinoline mediated by a dual bromide ion/TEMPO redox catalyst system,yielding the tetrahydroisoquinoline of the corresponding ketone.TEMPO can selective oxidate of C-N bond,provided a activated imine salt,and activation the C-H bond.Based on this research results,examining TEMPO oxidate tetrahydroisoquinoline and its derivatives,and activate the C-H bond adjacent of N atoms,realize the coupling reaction with other nucleophilic reagent.