The Preparation Of 2-Amino Pyrimidine And Study Of N-arylation Under The Catalysis Of Carboxylic Acid Copper

Nitrogen-containing heterocyclic aromatic compounds, as important intermediates, play indispensible role in the synthesis of pharmaceutical, biological and material molecules. Huge progress was made for the synthesis of these compounds in recent yeas, from the traditional Ullmann-Goldberg and Nitrate reduction methods to the amination of alkyl halide. The C-N crossing coupling reaction of aromatic primary amines, as an important project in organic chemistry, is widely invesitigated and applicated in material and medicine. Research to simpler and more efficient methods for the synthesis of aromatic primary amines and selective implementation C-N coupling with alkyl halides have aroused wide concern from the chemistry society.In this thesis, the latest development of the C-N coupling reactions of alkyl halides with aromatic primary amines were summarized; the methods to prepare aromatic primary amines from ammonia as amine source were briefly reviewed. And the reactions between aryl sulfonates and ammonia leading to the aromatic primary amines as products were investigated. Finally, we observed the C-N coupling reactions between these primary amines and alkyl halides catalyzed by copper.The specific research contents and results were described as follows:1. At room temperature, a series of aromatic primary amines were prepared from ammonia with aryl sulfonates in a non-toxic and green organic solvent, PEG400 as the PTC conditions. With this simple and green method, wide range of substrates can be tolerated giving to the desired primary amines products, including the nitrogen-containing heterocyclic compounds with strong electrical-withdrawing gourps.2. With the Copper(I) carboxylate/ 1,10-Phenanthroline as catalytic system, and the bromide/iodide halides as electrophiles, the N-single arylation of 2-amino pyrimidines can be achieved with K3PO4 as base, and the N-double arylation can be achieved with the t-Bu ONa as the base, respectively. Meanwhile, the influence of material ratio, reaction time, catalyst dosage and other factors upon the reactions were studied. A series of N-single/double aryl products were synthesized.All the products were characterized by 1H NMR, 13 C NMR and HRMS spectroscopic analysis.