Study On Arylation And Alkylation Of Aromatic Amines By Free-Transition Metal Catalysis

Nitrogen-containing compounds are ubiquitous in pharmaceutics,plastics,and functional materials.In recent decades,due to the rapid development of nitrogen-containing organic chemistry,the demand for nitrogen-containing compounds is increasing.The extraction of nitrogen-containing organic substances from natural products is no longer sufficient for the development of modern society.Compared with natural products,nitrogen-containing organic compounds obtained by organic synthesis have the advantages of designable diversity structure and relatively low cost.Therefore,finding an efficient,economical,and environmentally friendly method of constructing carbon-nitrogen bonds has become increasingly popular with chemists.With the development of green chemistry,the term "metal-free catalysis"has been well known,so the development of metal-free catalysis to construct C-N bond reaction is not only an efficient and economical synthesis path,but also meets the concept of green chemistry.Based on the above viewpoints,two metal-free methods were developed for the construction of C-N bonds in this thesis.Details are as following:1.N-aryl indolines were synthesized under metal-free conditions.A series N-aryl indolines can be achieved using indolines and nitrobenzene as the substrates in the condition of BuOK/DMF/-30?.No metal was used in this strategy and the reaction displays a broad substrate scope and good tolerance of a variety of substituents including halogen,alkyl,NO2 and COOH etc.2.Paraformaldehyde provides a carbon source to achieve N-alkylation and peroxidation of N-methylaniline.A series of N-((tert-butylperoxy)methyl)-N-methylaniline derivatives were generated in the presence of TBHP by using commercial paraformaldehyde as a carbon source and N-methylaniline derivatives in this reaction.The conditions are mild and the efficiency of conversion of paraformaldehyde is high without metal catalysis.It is a simple and efficient method for N-alkylation and peroxidation of N-methylaniline and its derivatives.In addition,diphenylamine and other kinds of aryl secondary amines are also suitable for this synthesis strategy.