Synthesis Of Triphenylphosphine Functionalized Organic Molecular Cage And Its Application In Olefin Hydroformylation Reactions

The hydroformylation of olefins is widely used in fine chemical and pharmaceutical fields.The main product,aldehyde,is an intermediate of many chemical drugs and reagents,and can be used to synthesize a series of compounds with wide application value such as carboxylic acid,alcohol and amine.At present,the Rh/PPh₃ homogeneous catalytic system occupies an important position in the industrial application of hydroformylation due to its high activity and good selectivity.Porous organic cages are a new class of porous organic materials.Because of their unique large steric hindrance cage structure,they can be directly used as special catalysts or ligands for catalytic applications by introducing coordination sites.Moreover,it has excellent solubility in some conventional organic solvents（such as ethyl acetate and dichloromethane）.This"solution processability"due to solubility provides an advantageous breakthrough for its application in catalytic reactions.By coordinating the solution processability of the porous organic cage with metal species,a novel catalytic material based on cage ligands can be prepared.In this paper,the triphenylphosphine structure is embedded in the organic molecular cage,and at the same time,the methyl group with the electron donating effect and the fluorine atom with the electron withdrawing effect are introduced to prepare four organic cage ligands meta-F-Cage,meta-2F-Cage,ortho-Me-Cage and meta-Me-Cage,and used in the hydroformylation of olefins to test their catalytic performance.Chapters 1 and 2 briefly summarized the development of porous organic cages and olefin hydroformylation reactions,summarized the design ideas and synthesis methods,and put forward the research purpose and significance of this paper.Finally,the supplies and analytical testing methods of the experimental part are introduced.Chapter 3,using fluorine atom and methyl substituted bromobenzaldehyde as starting materials,and protecting the carbonyl group with triethyl orthoformate to generate the corresponding acetal,then the corresponding aldehyde substituted triphenylphosphine monomer is generated by Grignard reaction.Finally,through imine condensation reaction with chiral cyclohexanediamine,four imine organic cages meta-F-Cage,meta-2F-Cage,ortho-Me-Cage and meta-Me-Cage with different electronic effects were prepared.Then use Nuclear magnetic resonance（NMR）,High resolution mass spectrometry（HRMS）,X-ray powder diffraction（PXRD）,Fourier transform infrared spectroscopy（FT-IR）,Thermogravimetric analysis（TG）,X-ray single crystal diffraction and other test methods to characterize the structure and stability of the organic cage ligand.In Chapter 4,the prepared meta-F-Cage,meta-2F-Cage,ortho-Me-Cage and meta-Me-Cage are respectively coordinated with rhodium to form a homogeneous Rh/Cage catalyst,which is applied in the 1-hexene hydroformylation reaction to explore its catalytic performance.It shows better catalytic activity and aldehyde selectivity than traditional catalysts and simple ligands（L1～L6）.Finally,the Rh/meta-Me-Cage homogeneous catalyst was selected to investigate the applicability of the substrate for the hydroformylation reaction of olefins,the results show that the catalyst has high catalytic activity and regioselectivity in the hydroformylation of 1-hexene,1-octene,1-heptene and styrene.