Synthesis And Heterogeneous Catalytic Application Of Quinoline And TEMPO Functionalized Porous Organic Polymers

Porous organic polymers(POPs)are emerging porous solids with high porosity,low density,diverse composition,easy functionalization and high stability.The properties of POPs can be well modulated by the introduction of functional units in the synthesis process;meanwhile,it is also easy to functionalize POPs via chemical modification.These advantages make POPs serve as excellent solid platforms for heterogeneous catalysis.Accordingly,the main contents of this thesis are centred around the synthesis and modification of the POPs,and utilization them for the heterogeneous catalysis.Accordingly,the main achievements could be divided into the following two parts:1.Synthesis of quinoline functionalized porous organic polymers(Q-CMPs)via the visible-light induced C_sp3-H functionalization reaction.Starting from glycine ester and alkynes,Q-CMP were synthesized directly via the visible-light induced C_sp3-H functionalization reaction under mild conditions(room temperature,atmosphere and visible light).This is the first time that visible light induced C_Sp3-H functionalization reaction has been applied to the synthesis of porous organic polymers.Compared with the traditional synthesis methods,this method has the advantages of mild reaction conditions,environmental protection,atomic economy and so on.This polymer has photocatalytic properties without any other chemical modifications.Under the irradiation of 5W Blue LEDs,Q-CMP can efficiently catalyze the cross-dehydrogenation coupling(CDC)reaction between glycine ester and indole,as well as the CDC reaction of 2-phenyl-tetrahydroisoquinoline with nitroalkanes or ketones.Furthermore,Q-CMP-1 can be reused for at least seven times with no obvious decrease of activities.2.Synthesis and catalytic application of TEMPO-functionalized ordered mesoporous polymers.The ordered mesoporous polymer FDU-15 was selected as the solid platforms for the heterogeneous catalyst.Firstly,the azide group was introduced into the channel of FDU-15 through chloromethylation and azidylation,then the small molecular catalyst TEMPO was further immobilized into the channel of FDU-15through"click"chemistry to obtain TEMPO-functionalized ordered mesoporous polymer catalyst(FDU-15-TEMPO).FDU-15-TEMPO can efficiently catalyze the oxidation of alcohol(70-97%yield)and the aerobic oxidative synthesis of 2-substituted benzoxazole and benzoimidazole(89-92%yield),and the catalyst can be reused for at least six times with no obvious decrease of activities.