CuSO₄·5H₂O/NaAsc Or CuTC-catalyzed C-N Coupling Reaction Of Aryl Halides With Aqueous Ammonia/Amides/Primary Aromatic Amines

Among nitrogen-containing compounds, anilines are important structural motifsfound in numerous natural products which had great influences on the fields ofpharmaceutical, biological, and material sciences. However, the traditionalpreparation of anilines mainly depended on Ullmann-Goldberg coupling reaction andnitrate reduction method for many years. The C-N crossing coupling reaction is veryimportant in organic chemistry and is widely used in chemical industry andpharmaceuticals. Therefore, careful choice of a simple and efficient method for thesynthesis of anilines by C-N crossing coupling reaction constitutes an area ofconsiderable interest.The latest development of the synthesis of anilines is summarized in this thesis.Furthermore, we developed three different new methods of the synthesis of anilines.The main research contents and results were as follows:1. CuSO4·5H2O/sodium ascorbate catalyzed cross-coupling reaction of arylhalides with aqueous ammonia for the synthesis of primary aromatic amines has beendeveloped. Key to the success included the application of aqueous ammonia under ahomogeneous condition. The easy use of aqueous ammonia and the use of nontoxicL-ascorbic acid sodium salt as a reductant are great advantages in terms of greenchemistry.2. CuSO4·5H2O/sodium ascorbate-catalyzed intermolecular C-N bond-formingreactions between aryl iodides and amides are described, which is both cheap andnontoxic, as the additive. A variety of functionalized amides including some practical,unique secondary amides, such as N-arylacrylamides, which are difficult to obtain bythe classical methods, are prepared. We have developed a simple, novel and efficientmethod for N-arylation of amides. Furthermore, some tertiary amides are prepared byusing copper thiophenecarboxylate.3. N-arylation of amides and anilines with aryl iodides was efficiently catalyzedby CuTC under ligand-free conditions with good to excellent yields. A variety ofsubstituted aryl iodides, amides, anilines and4-aminoantipyrine were found to beapplicable to the simple catalytic system. At the same time, the effects of materialratio, reaction time, catalyst and its dosage on the reaction were investigated. All the products were confirmed by elemental analysis,1H NMR,13C NMR andHRMS spectroscopic analysis.