Study On Tandem Rearrangement Reaction Of Arylhydroxylamines With Phosphorus-containing Compounds

Phosphorus-containing compounds have many special properties such as multi-valent and easy coordination,which are numerous and widely used in agriculture,medicine,materials,chemical synthesis,and other practical fields.For example,phosphates are often used in the synthesis of prodrugs and phosphorus-containing flame retardants;Phosphonyl compounds are often used as ligands for asymmetric catalytic reactions.As a class of special compounds with N-O bond structure,arylhydroxylamines are prone to rearrangement reaction related to N-O bond cleavage,so as to realize the construction of new chemical bonds and complete the synthesis of new substances.The tandem rearrangement reaction of arylhydroxylamines with phosphorus-containing compounds is an important means to introduce phosphorus into the arylhydroxylamine system,which is a significant method for the synthesis of novel organic phosphine compounds containing aromatic amine skeleton.This thesis is divided into three parts:In the first part,the rearrangement reactions of arylhydroxylamine and its derivatives are briefly introduced.Hydroxylamine,O-arylhydroxylamine,N-oxide,etc.can generate N,Oactive intermediates by reacting with other substances,causing[3,3]-σ rearrangement,[2,3]-σrearrangement,[1,3]-σ rearrangement and other reactions to construct functionalized aromatic amine compounds,biaryl compounds,etc.The research progress in the construction of phosphates based on O-phosphonylation of phosphorus-containing compounds such as phosphine halides,phosphine oxides,phosphate compounds was also introduced in detail.Finally,the research results of arylphosphonylation are briefly introduced,such as Hero coupling reaction.In the second part,we developed a tandem Atherton-Todd/[3,3]-σ rearrangement reaction based on arylhydroxylamines and dialkyl phosphites.In this study,the P(O)-Cl species generated in situ through the Atherton-Todd reaction of dialkyl phosphites and CCl4 may be captured by arylhydroxylamines to afford O-phosphorylated intermediates,which could further rapidly undergo[3,3]-rearrangement to afford ortho-phosphated aromatic amines.In the third part,we tried to construct O-phosphonylation intermediate by the reaction of arylhydroxylamines and diphenyl phosphine chloride or diethyl chloridophosphite,and then complete the[2,3]-σ rearrangement reaction through N-O bond cleavage and C-P bond formation to synthesize ortho-phosphorylated aromatic amines.At present,the optimization of reaction conditions and the investigation of substrate universality in this work are still underway.The thesis discussed the tandem rearrangement reactions of arylhydroxylamines with phosphorus-containing substrates,synthesized two types of compounds,ortho-phosphated aromatic amines and ortho-phosphorylated aromatic amines by constructing O-P and C-P,respectively.These research results enrich the synthesis methods of organic phosphine compounds containing aromatic amine skeleton and are conducive to biological activity screening and other expanded-application research.