Study On Hydrogen-Borrowing And Dehydrogenation Coupling Catalyzed By Copper-Based Porous Materials

With the understanding of the growing global energy demand and environmental constraints,it is becoming more and more necessary to develop"green"（sustainable）chemical processes and transformations.In the traditional catalytic system,homogeneous catalyst has a series of development because of its relatively uniform active center,high selectivity to reaction and less side reactions.However,this kind of catalyst is gradually exposed that it is difficult to separate,recover and regenerate from the reaction,which will cause pollution to the environment and so on.Therefore,the introduction of heterogeneous catalysts with high catalytic activity and environmental friendliness has important research value.Since the 21st century,porous materials have attracted extensive attention due to its excellent properties such as large specific surface area and modifiable activation center.Metal organic framework materials and mesoporous molecular sieves materials were selected as objects to investigate and study its research status.The aim is to use copper-based supported catalysts with porous structure to catalyze hydrogen borrowing reaction and dehydrogenation coupling reaction to prepare a series of nitrogenous compounds with biological activity,and carried out the recovery and reuse of the catalyst and stability experiments,which greatly reduce the reaction loss.1.Using copper-based skeleton compounds as precursors,the carbon-based skeleton carrier material Cu-PC@OFM with octahedral configuration was prepared by calcining it at high temperature.The carbon carrier obtained was used as an inert medium to make the metal active component Cu（I）nanoparticles highly dispersed.Through the hydrogen borrowing reaction of alcohols and amines catalyzed by the material,a series of secondary amines were synthesized in medium to good yield,showing high substrate applicability and good recyclability.The structures of all the target products were confirmed,that was ¹H NMR and¹³C NMR characterization.2.A kind of bimetallic supported mesoporous material SBA-15 was introduced,which was smodified by copper and aluminum respectively to obtain mesoporous molecular sieve Cu/Al-SBA-15.By controlling the valence of copper-based oxides and leading to the dehydrogenation coupling of o-aminothiophenol and benzyl alcohol,a series of benzothiazoles were synthesized efficiently by“one-pot method”.It also had the characteristic of separating the catalyst from the system and putting it back into the reaction.The structures of all the target products were confirmed,that was ¹H NMR and ¹³C NMR characterization.3.Another bimetallic mesoporous material Cu/Al-SBA-15（I）was introduced to prepare novel skeleton 2H-benzotriazole derivatives by one-pot method for the first time.In this respect,amino-containing benzotriazole derivatives were synthesized by one-step method using o-phenylenediamine as substrate,and the reaction was completed within 4 hours.The structures of all the target products were confirmed,that was ¹H NMR,¹³C NMR and HRMS characterization.After that,the fluorescence of benzotriazole decreased under the acylation of acyl chloride.