Study On [TBA][P（SiCl₃）₂] As Phosphorus Source For The Synthesis Of Phosphorotrithioates And 1,2,4-Diazaphosphole

Phosphorus is one of the six basic"biological elements"and is an important component of organic compounds.In recent years,organophosphorus compounds（OPCs）have been widely used in many fields such as biochemistry,materials chemistry and synthetic chemistry,therefore becoming research focal points.Usually,the synthesis of organophosphine compounds is a multi-step,energy-intensive,hazardous to operate,reagents difficult to handle,and environmentally unfriendly process,which has prompted the development of green and gentle methods for the synthesis of organophosphine compounds.On this basis,this thesis briefly summarizes the synthesis methods of phosphorothioesters and common five-membered phosphorus heterocyclic compounds,followed by the design of[TBA][P（SiCl₃）₂]as an inorganic phosphorus source for the construction of organophosphine compounds,the following are the main studies and results:In the first part,we prepared a series of phosphorotrithioates quickly and easily by using[TBA][P（SiCl₃）₂]as a new inorganic phosphorus source,I₂ as an additive,K₂S₂O₈ as an oxidizer,and reacting directly with various disulfides in the presence of K₃PO₄.The method is operationally simple,mild reaction conditions,environmentally green and friendly.In the second part,we initially explored the NEt₃-promoted cyclization reaction of[TBA][P（SiCl₃）₂]with chlorohydrazones,leading to the synthesis of various substituted 1,2,4-diazaphosphorus cyclopentadiene derivatives.This method is not only a new strategy for the synthesis of such compounds,but also a further development of the construction of P-C bond reactions using[TBA][P（SiCl₃）₂]as an inorganic phosphorus.In addition,the target product obtained by this method is a trivalent phosphorus compound,which also provides the possibility of subsequent modification.The molecular structure of the above target product was confirmed by ¹H NMR,¹³C NMR,³¹P NMR,¹⁹F NMR and HRMS characterization.