Copper Catalyst Immobilized On Organic Polymeric Materials For The Synthesis Of Nitrogen-containing Compounds

Biologically active nitrogen-containing compounds are among the most important ones in heteroatom compounds.It is worth noting that quinoxalines and propargylamines are the most important nitrogen-containing compounds according to the research on biologically activity of nitrogen-contatining compounds compared with natural analogues.Furthermore,quinoxalines and propargylamines can be used in many fields like organic synthetic chemistry,biopharmaceuticals,agriculture,and advanced material synthesis due to its unique chemical and biological activities.Thus,they have an attracted significant attention from scientists to develop novel and effective strategies to synthesize these molecules.It has been proved by a great deal of experimental results that the versatile multicomponent reaction?MCR?strategy provides a new approach for the synthesis of such nitrogen-containing compounds.Multicomponent reaction is a kind of simple and effective protocol without need of separating intermediates to directly afford the final products.In addition,due to the excellent properties of organic polymers,their application in industrial and academic community have developed rapidly in recent years,and organic polymers are playing an increasingly important role in the field of catalysis and synthesis.The main content of dissertation involves how to prepare efficient and simple heterogeneous catalysts based on organic polymeric materials and its application in organic synthesis and catalysis.This thesis includes following parts:1.Firstly,polyvinyl chloride?PVC?and ethylene diamine?EDA?were employed as raw materials to prepare EDA functionalized PVC?EDA-PVC?.The EDA-PVC contains a large number of amino groups which can strongly chelating with transition cations.Secondly,EDA-PVC was immersed in a mixed solution of Pd^II and Cu^II cations at room temperature to provide a Pd^II/Cu^II@EDA-PVC bimetal catalyst.This bimetallic catalyst was demonstrated as efficient catalyst promoting the transformation of diphenylacetylene or substituted diphenylacetylene to dicarbonyl compounds through Wacker oxidation and then further initiated the condensation of the resultant dicarbonyl compounds with o-phenylenediamine or substituted o-phenylenediamine to produce quinoline derivatives.2.Firstly,PAA/PVC mesoporous hybrid fiber was prepared via a simple phase inversion process by extrude PAA/PVC solution of DMF into mixed solution of water and methanol.Secondly,Cu^II@PAA/PVC mesoporous hybrid fiber composite was prepared by metathesis between carboxylate of PVC/PAA and Cu^II in copper sulfate solution.According to experimental results,Cu^II@PAA/PVC can effectively exert in the A₃,KA₂,and decarboxylized A₃ coupling reactions for the synthesis propargylamines.3.Initially,we use the p-toluenesulfonic acid?PTSA?and paraformaldehyde to prepare co-polymer of p-toluenesulfonic acid-formaldehyde?PTSAF?which contain a large number of sulfonic acids groups.And then an acid-base reaction between PTSAF and PEI is performed to prepare PEI/PTSAF support with a large of amine groups.Finally,in the aqueous solution,PTSAF/PEI is used to chelate with Cu^II to obtain Cu SO₄@PEI/PTSAF nanocatalyst.This nanocatalyst was found to be an efficient catalyst for A₃ reaction and decarboxylated A₃ reaction to synthesiz propargylamines in one-pot.In this work,three kinds of novel heterogeneous catalysts based on high-performance organic polymeric material have been synthesized.Meanwhile,these heterogeneous catalysts have been applied in the synthesis of a series of quinoxalines and propynylamines.