Applications Of MOF-derived Catalysts For The Synthesis Of N-arylsulfonamides And The Dehydrogenation Of Primary Amines

Each breakthrough in the field of catalysts has greatly promoted the development of the chemical industry.Therefore,continuous research on new catalysts is of great significance to modern industry.Metal organic frameworks(MOFs)have huge application potential and development prospects in the field of catalysis due to their structural characteristics such as porosity,high specific surface areas,and many coordinatively unsaturated metal sites.In this thesis,MIL-101(Fe)was used as a catalyst for the synthesis of N-arylsulfonamides,the active sites of catalysis are coordinatively unsaturated iron sites on MIL-101(Fe).Ui O-66(Ce)supported Ru nanoparticles as a catalyst which was used in the reaction of dehydrogenation of primary amines to nitriles without acceptor,the active sites of catalysis are Ru nanoparticles which were encapsulated in Ui O-66(Ce)First of all,the application of MIL-101(Fe)in the synthesis of N-arylsulfonamide was studied.A newly developed chemoselective reaction of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes has been disclosed.The chemistry,in which non-toxic water and recyclable iron-based metal-organic frameworks are employed as the solvent and catalyst,respectively,provides an efficient approach for the generation of N-arylsulfonamides.Due to N-arylsulfonamides are widely present in biologically active compounds and drugs,three biologically active compounds were also successfully synthesized using this method,rendering this methodology attractive to both synthetic and medicinal chemistry.Subsequently,the application of MOFs-encapsulated noble metal catalysts in the reaction of acceptorless dehydrogenation of primary amines to nitriles was explored.A recyclable Ui O-66(Ce)encapsulated Ru nanoparticles catalyst was prepared,which can effectively catalyze the reaction of acceptorless dehydrogenation of primary amines to nitriles in the aqueous phase.Introduction of metal Ru to Ui O-66(Ce)contributes to the formation of Lewis acid-base pairs [Ru-O-Ce-Vo?] on the catalyst owing to the metal-support interaction,acting as active sites of catalysis,which can absorb and activate amines,while promoting hydrogen transfer and accelerating the reaction.