Preparation Of Fiber Polymer(Pd/M)Bimetallic Catalyst And Catalytic Performance For Coupling Reaction Of Phenylacetylene With Csp~2

The transition metal catalyst has important research significance in the field of organic synthesis,and it has application value in the fields of pharmaceutical intermediates,pesticides,optoelectronic materials,fine chemicals and so on.In this paper,the Amidoxime fibers(AOFs)were used as substituents to replace the active small molecules,and two kinds of metals(Pd/M)were arranged on the surface of the fibers to synthesize the bimetallic catalysts(Pd/M-AOFs).The bimetallic catalysts were then used in Sonogashira coupling reaction,which included halogenated aromatic hydrocarbons with phenylacetylene,heterocyclic aromatic hydrocarbons with phenylacetylene,bromostyrene with phenylacetylene.And obtain some research results:(1)(Pd/M-AOFs)was prepared by the coordination of Amidoxime fiber with palladium,iron,copper and nickel active metal with catalyzed Sonogashira coupling reaction.(2)(Pd/M-AOFs)catalyst was used to catalyze the coupling reaction of iodobenzene with phenylacetylene and investigate the effect of different catalysts on the yield of coupling reaction.It was found that when use Pd(?)/Ni(?)-AOFs bimetallic complex catalyst,the highest yield.Optimize the process conditions,to obtain the best reaction conditions:iodobenzene(2 mmol),phenylacetylene(2.5 mmol),solvent(ethylene glycol,20 mL),base(sodium hydroxide,5 mmol)reaction temperature(60?),Pd(?)/Ni(?)-AOFs(0.8 mol%,3 mol%,0.10 g).Pd(?)/Ni(?)-AOFs catalysts have very good catalytic activity and can still achieve 90%yield in 4 times.And the reaction has a high catalytic activity for different electron-donating and electron-withdrawing reactants.(3)The amidoxime fiber bimetallic complex(Pd/M-AOFs)catalyst was used to catalyze the coupling reaction of 2-bromopyridine with phenylacetylene and then investigate the effect of different catalyst on the yield of coupling reaction.It was found that the highest yield was obtained when Pd(?)/Ni(?)-AOFs bimetallic complex catalysts were used.The optimum reaction conditions were obtained:2-bromopyridine(1 mmol),phenylacetylene(1.5 mmol),solvent(ethanol:water=2:1,20 mL),base(Potassium carbonate 2 mmol),Reaction temperature(70?),reaction time(2 h),Pd(?)/Ni(?)-AOFs(0.4 mol%,2 mol%,0.10 g).Pd(?)/Ni(?)-AOFs catalysts have very good catalytic activity and can still achieve 80%yield in 4 times.And the reaction has a high catalytic activity for different electron-donating and electron-withdrawing reactants.(4)The amidoxime fiber bimetallic complex(Pd/M-AOFs)catalyst was used to catalyze the coupling reaction of 3-bromoquinoline with phenylacetylene,and then investigate the effect of different catalyst on the yield of coupling reaction.The results show that when the use of Pd(?)/Ni(?)-AOFs bimetallic complex catalyst,the highest yield.The optimum reaction conditions were obtained:3-bromoquinoline(2 mmol),phenylacetylene(3 mmol),solvent(water,20 mL),base(sodium hydroxide),reaction temperature(80?),Reaction time(7 h),Pd(?)/Ni(?)-AOFs(0.6 mol%,3 mol%,0.10 g).Pd(?)/Ni(?)-AOFs catalysts have very good catalytic activity and can still achieve 80%yield in 4 times.And the reaction has a high catalytic activity for different electron-donating and electron-withdrawing reactants.(5)The amidoxime fiber bimetallic complex(Pd/M-AOFs)catalyst was used to catalyze the coupling reaction of bromostyrene with phenylacetylene and then investigate the effect of different catalysts on the yield of coupling reaction.When the Pd(?)/Ni(?)-AOFs bimetallic complex catalyst is used,the yield is highest.The optimum reaction conditions were obtained:bromostyrene(2 mmol),phenylacetylene(2.5 mmol),solvent(dimethylformamide,20 mL),base(sodium carbonate),reaction temperature(100?),Pd(?)/Ni(?)-AOFs(0.8 mol%,3 mol%,0.10 g),reaction time(8 h).In this paper,the carrier function of amidoxime fibers solves the problem that the traditional homogeneous catalyst has a low recovery rate.Ligand substitution replaces the complexes that are difficult to synthesize or are sensitive to air-sensitive inert gases,while the coordination of N and O enhances the coordination of the central metal's electrons,the steric hindrance of the fiber ligands,and Coordination of the role of positioning,is conducive to product selectivity.The catalyst preparation process is simple,the raw materials are cheap and easy to obtain,the reaction conditions are mild,the economic cost and the environmental pollution are reduced,and a new catalyst for the environmental protection and practical application value is explored for the coupling reaction.