Studies On The Green Synthesis Of Some Organic Phosphine Compounds With Alcohol As Direct Material

Organic phosphines are an important kind of organic compounds,which exists widely in some natural products and drug molecules.They are important intermediates and commonly used catalysts in organic reactions.Their excellent properties have led to the development of methods for the synthesis of different types of organic phosphine compounds.In these methods,it is often necessary to use toxic starting materials,expensive metal catalysts,need strong acid,strong alkali,superhigh temperature,superlow temperature and other harsh conditions,and the substrate scope is limited.The development in the synthesis of organic phosphine compounds green,efficient and economical method has always been an important topic in the field of modern organic synthesis.In this paper,the synthesis method of organic phosphine compounds was studied by using green alcohol as direct material.It consists of three parts:Part I:Study on the TMSOTf catalyzed synthesis of organic phosphine compounds containing C-P（O）bond by the reaction of phosphite esters with various alcohols.We reviewed the synthesis methods of organic phosphine compounds containing C-P（O）bond and found that Arbuzov reaction and its improved method have some problems,such as high toxicity of raw materials and the substrate scope is limited.Based on the existing research of our group,a new,green,efficient,practical,high universal Arbuzov reaction,TMSOTf-catalyzed organic phosphine compound synthesis method was developed,which can be used not only for primary alcohols,but also secondary alcohols,tertiary alcohols.Part II:Synthesis of organic phosphine compounds with C-P（O）bond by Cu（OTf）₂catalyzed disubstituted phosphine oxide with various alcohols by high universal dehydration P-alkylation reaction.Through literature investigation,we found that the existing dehydration P-alkylation reaction of dissubstituted phosphine oxide and alcohols are mostly only applicable to active alcohols,and lack of a high universal method.A Cu（OTf）₂-catalyzed dehydration P-alkylation reaction of disubstituted phosphine oxide with various alcohols was developed to synthesize organic phosphine compounds containing C-P（O）bonds.PartⅢ:Research on the synthesis of thiophosphonate compounds.We review the synthesis methods of thiophosphonate,and found that most of these needed the participation of organic sulfur compounds or organic halides,and lacked of a green,clean and efficient synthesis methods.Therefore,we hope to develop an acid-catalyzed synthesis method of thiophosphonate using green alcohols,elomeric sulfur and P（O）H compounds as direct materials.