Study On The Synthesis And Ability For Ion Sensing Of Ferrocene Ligands And Synthesis Of Ferrocene Indenes

In this thesis,ferrocene containing phosphine ligands,ferrocene containing Ntosyl hydrazone ligands and the ferrocene containing N-phosphinic hydrazide ligands were synthesized.Ion recognition performance of the ferrocene containing N-tosyl hydrazone ligands and ferrocene containing N-phosphinic hydrazide ligands were studied.In addition,planar chiral ferrocene indene compounds were also synthesized.The details are as follows:1.Synthesis of Ferrocene-based Phosphine Ligands via Cu-catalyzed Reductive Coupling of Ferrocenyl Ketone-derived Tosylhydrazones and H-phosphorus OxidesCurrently,ferrocene phosphine ligands have a wide range of applications in transition metal catalyzed coupling reactions and asymmetric catalysis reactions,but their synthesis often requires sensitive reagents such as alkyllithium reagents,cumbersome synthetic routes and resolution steps.Therefore,in designing new ferrocene phosphine ligands,it is important to use inexpensive and readily available materials and fewer synthetic steps.In this paper,ferrocene-containing phosphine oxides having various substituents on a phosphorus atom were obtained by a Cu-catalyzed reductive coupling reaction of a ferrocenone-derived N-tosyl hydrazones and an H-phosphorus oxides.Subsequent reduction of the ferrocenylphosphine oxide gives 1-substituted ferrocene phosphine ligand 7 and 1,1’-disubstituted ferrocene phosphine ligand 9.Josiphos-type ligand 8 was synthesized by lithiation of 7 in the ortho position and quenching with diphenylphosphine chloride or dicyclohexylphosphine chloride.This method provides a new approach to the synthesis of ferrocene phosphine ligands.2.Synthesis of Ferrocene Containing N-Phosphinic Hydrazides and the Application as Chemosensors for Cu2+ and Hg²⁺ IonsDue to the presence of conversion between Fe2+ and Fe3+ in ferrocene,the ferrocene derivatives have a unique redox potential in electrochemistry.In recent years,quite a number of ferrocene-containing electrochemical sensors containing N or O as recognition units have appeared.The ferrocene containing N-phosphinic hydrazide has two N atoms and one O atom at the same time as a recognition unit.However,the use of a ferrocene containing N-phosphinic hydrazide as an electrochemical sensor has not been reported in the literature,which may be due to the small number of methods for synthesizing ferrocene containing N-phosphinic hydrazide.In this paper,the method of constructing N-P bond by metal-free coupling reaction of ferrocene containing Ntosyl hydraone with H-phosphorus oxide was used to synthesize 1-substituted and 1,1’-disubstituted ferrocene containing N-phosphinic hydrazides 3 and 5 in medium or higher yields.And the structures of the products 3a,3f and 3i were determined by single crystal diffraction experiments.The cation recognition properties of ferrocene containing N-phosphinic hydrazides 3a and 5a were investigated by electrochemical,UV-visible absorption spectroscopy and 1H NMR titration.Ligands 3a and 5a can selectively recognize Hg²⁺ and Cu2+ ions.After the addition of Hg²⁺ ions,the color of 3a and 5a in the solution changed from light yellow to red,and the color of the solution changed from pale yellow to yellowish green after adding Cu2+,which can be easily detected by naked eyes.3.Ferrocene Containing N-tosyl Hydrazones as Optical and Electrochemical Sensors for Hg²⁺,Cu2+ and F-IonsHg²⁺ is one of the most toxic metal ions in heavy metal ions,which can be easily absorbed and accumulated by the organism from the environment and cause damage to DNA,cell mitosis,central nervous system and endocrine system.In addition,excessive Cu2+ ions may cause a variety of neurological diseases.On the other hand,F-ion is a particularly important biologically functional anion,but excessive intake can lead to fluorosis and tooth discoloration.Recently,hydrazone functional groups have been shown to be versatile ion recognition units for cations and anions due to their functional diversity.In this paper,1-substituted and 1,1’-disubstituted ferrocene containing N-tosyl hydraones 2a and 2b were synthesized as electrochemical sensors and were characterized by 1H NMR,13 C NMR,ESI-MS and X-ray single crystal diffraction.The cation and anion recognition properties of 2a and 2b were investigated by electrochemical,UV-visible absorption spectroscopy and 1H NMR.The chemical sensors 2a and 2b can selectively recognize Hg²⁺,Cu2+ and F-ions.After the addition of Hg²⁺ ions,the color of the solutions of 2a and 2b changed from light yellow to red,while the color of the solution changed from light yellow to yellowish green after the addition of Cu2+.Therefore,ligands 2a and 2b can be used for naked eye detection.4.Synthesis of Planar Chiral Ferrocene[2,3a]IndeneIndene is a common carbocyclic skeleton in natural products,and is widely used in biology,medicine,materials and other fields due to its unique structure and properties.Ferrocene [2,3a] indene has the characteristics of planar chirality and can be used as a skeleton of planar chiral ligands.In this paper,Pd（OAc）2 was used as the catalyst,（Ra）-Segphos was used as the chiral ligand,potassium carbonate was used as the base,and pivalic acid was used as the additive to synthesize planar chiral ferrocene [2,3a] indene.The production yields reached 99% and the enantioselectivity reached 1:99 er.The reaction produces planar chiral ferrocene [2,3a]indene compounds having various electron withdrawing groups and electron donating groups on the benzene ring in a medium or higher yield and enantioselectivity.