Synthesis And Application Of Sulfonylated Arylamines

It is well known that arylamines are a class of nitrogen-containing organic functional molecules with unique properties,which exist in many natural products,synthetic drugs,organic materials and agricultural chemicals,and have very extensive and important applications in many fields.Sulfones,especially aryl sulfones,also play important roles in many bioactive drugs,catalysts,and functional materials.Compounds containing aryl sulfone structures are currently extensively applied in the field of medical treatment,such as the treatment of leprosy,schizophrenia,depression,hepatitis and heart disease,which also makes the related research on the synthesis of aryl sulfones received extensive attention.Sulfonylated arylamines have the characteristics of both aromatic amines and sulfones,and have more important synthetic value.They are not only the basic structural units of various bioactive molecules and natural products,but also can be used as organic intermediates for building other functional molecules.N-arylhydroxylamine contains a N-O bond that is very easy to break,and the rearrangement reaction can occur to obtain various functionalized arylamine compounds.This thesis will focus on exploring the reaction of N-arylhydroxylamines with trifluoromethylsulfinyl chloride to form ortho-trifluoromethanesulfonylated arylamines,and conducting in-depth research on the reaction mechanism and the application of the product.This thesis is mainly divided into the following three parts.In the first part,a brief overview of the recent research progress in the synthesis of sulfones is summarized.The main synthetic methods include oxidation with strong oxidants,SO2 insertion,metal-catalyzed C-H bond activation,and coupling reactions;Secondly,a survey involving the rearrangement reaction of N-O cleavage was carried out to summarize the three types of rearrangement reactions of hydroxylamine compounds,which includes[3,3]-a rearrangement,[2,3]-σ rearrangement and[1,3]-σ rearrangement.In the second part,N-arylhydroxylamine compounds can react with trifluoromethylsulfinyl chloride to form ortho-trifluoromethanesulfonylated arylamines.N-Arylhydroxylamine undergoes an unconventional O-trifluoromethylsulfinylation reaction with trifluoromethylsulfinyl chloride with high selectivity,followed by a rapid concerted[2,3]-σ rearrangement and rearomatization to yield ortho-trifluoromethanesulfonylated arylamines,which has been confirmed by controlled experiments and density functional theory(DFT)calculations.This sample and rapid transformation proceeded smoothly with good yields and excellent ortho-selectivity in the absence of any metals,ligands and external oxidant.The discovery of this reaction provides a new idea for the synthesis of sulfone compounds and has important theoretical significance.In the third part,trifluoromethanesulfonylated arylamines have good prospects for industrial applications and can be used as intermediates for the synthesis of various functional molecules or organic fragments.The amino and sulfonyl groups of trifluoromethanesulfonylated arylamines can each independently participate in the reaction,thereby transforming into other important functional organic molecules.The yields of these conversion processes are generally relatively high,reflecting the high practical value and good potential of trifluoromethanesulfonylated arylamines in industrial synthesis,which has a certain practical significance.In this thesis,a series of structurally diverse ortho-trifluoromethanesulfonylated arylamines were rapidly and efficiently constructed through the tandem[2,3]-σrearrangement reaction between N-arylhydroxylamine and trifluoromethylsulfinyl chloride.It can be effectively transformed into a series of functionalized molecules with different properties under different reaction conditions,and has a very good prospects for industrial applications.This tandem rearrangement reaction is rarely reported and has the potential to be extended to the efficient synthesis of other types of sulfones.