Synthesis Of ?-aminophosphonates Catalyzed By Transition Metal Complex Of Benzenesulfonic Acid

Sulfonic acid compounds have been applied in catalysts,dyes,electroplating and surfactants fields for a long time.In addition,they have potential applications in liquid crystals and nonlinear optical materials.All the oxygen atoms of the SO₃^-group can coordinate with metal ion.Because the coordination modes of the metal sulfonates are diversified and modified,their coordination structures are variable.They are widely used in electroplating industry,electrochemistry,surfactant and other fields.As a type of novel Lewis acids,metal sulfonates have been widely used in various organic synthesis in recent years due to their advantages such as good stability,good catalytic performance,and non-decomposition in water and recyclability.In this paper,the research progress of the synthesis and application of metal sulfonates and?-aminophosphonate derivatives are reviewed.Four transition metal Complex of benzenesulfonic acid of zinc benzenesulfonate,cadmium benzenesulfonate,zinc p-toluenesulfonate and cadmium p-toluenesulfonate were synthesized,and their structures were characterized by IR,TG and X-ray single crystal diffraction.The catalytic property of them in Kabachnik-Fields reaction was investigated.The reaction mechanism was subjected to density functional theory?DFT?by Gaussian 09 software.The main research contents are as follows:1.The crystals of the four transition metal benzenesulfonates were obtained by solvent evaporation method.The structures were characterized by various analytical methods such as IR,TG and X-ray single crystal diffraction.Each metal ion in zinc benzenesulfonate,cadmium benzenesulfonate and zinc p-toluenesulfonate all forms a deformed octahedral spatial configuration with six coordination waters.The cadmium ion in cadmium p-toluenesulfonate coordinates with five coordination waters and an oxygen atom of one p-toluenesulfonic acid group.2.The catalytic property of the above four transition metal benzenesulfonates was investigated.A series of?-phosphoramidate derivatives were efficiently synthesized by an one-pot three-component reaction of aromatic aldehyde,aromatic amine and diethyl phosphite?naromatic aldehyde:naromatic amine:ndiethyl phosphite=1:1:1.2?catalyzed by 0.25 mmol catalyst at 40 ^oC under solvent-free conditions.The method has the advantages of solvent-free condition,high catalytic activity,reusability,and environmental friendliness.3.The contribution of charge distribution and molecular fragmentation to molecular orbitals and the structure of zinc benzenesulfonate,cadmium benzenesulfonate,zinc p-toluenesulfonate and cadmium p-toluenesulfonate were calculated by using the density functional theory?DFT?with the Gaussian 09software package.The 6-31G?d?basis set is used for the C,H,O and S atoms at the B3LYP level,and the SDD basis set is used for the Zn and Cd atoms.The calculated results were verified by comparing them with experimental data.The reaction mechanism of Kabachnik-Fields was clarified by quantum chemical calculation.