Study On New Synthesis Methods Of O-amino Arylphosphine Oxides And Aryl Quaternary Phosphonium Salts

Organophosphorus compounds play an important role in the fields of organic synthesis,materials chemistry,medicinal chemistry and life sciences.Creating new organophosphorus compounds and discovering their potential efficacy have been a constant goal of organophosphorus chemists.The o-amino arylphosphine oxides have a potential effect on the treatment of obesity and cancer.The aryl quarter phosphonium salts can be used as a phase transfer catalyst and have broad prospects for treating leukemia and designing mitochondrial targeted drugs.The construction of organophosphorus compounds through transition metal catalysis can introduce various functional groups,but there are some problems,such as poor tolerance of functional groups,harsh reaction conditions,moisture-sensitive substrates and poor selectivity.Therefore,it remains to be further developed in constructing valuable organophosphorus compounds via mature transition metal catalysis methods.In this paper,a new method for transition metal catalyzed benzotriazoles and tri-coordination phosphorus to construct o-amino arylphosphine oxides and aryl quaternary phosphonium salts is mainly studied.Th e main contents are as follows:1.Study on the palladium or nickel-catalyzed denitrogenative phosphonylation of benzotriazoles and phosphites,which can obtain a series of valuable o-amino arylphosphine oxides.According to DF1 calculation,the reaction went through a key four-memnered palladacycle intermediate.Various benzotriazoles and phosphites work well and this method has the potential to large-scale production.The product can be reduced to form a precursor of bidenate aminophosphine ligand--o-aminotriphenylphosphine and a large conjugated phosphorus substituted fluorene structure can be formed after oxidation,which provides a new strategy for the synthesis of photoelectronic materials.This method has the advantages of wide range of substrates and simple reaction conditions.2.A new method of palladium-catalyzed synthesis of aryl quaternary phosphonium salts from benzotriazoles and triaryl phosphorus is studied.This method does not require the use of substrates which sensitive to moisture and oxygen.It also has the advantages of good functional group tolerance,simple operation,short reaction time and high yield and it could get compounds with novel structure.