Synthesis Of1,2-diamine And β-fluoro Amine Using Aziridine As Substrate

Three-membered heterocyclic compounds such as aziridines are very important organic intermediates, and have wide applications in organic synthesis. Valuable1,2-difunctional compounds can be obtained by ring-opening of them with nucleophiles.This thesis consists of three chapters. The first chapter summarized the ring-opening reactions of aziridines under different conditions. The ring-opening reactions of aziridines with nitrogen-containing nucleophiles and fluorine-containing nucleophiles were the focus of the review. The design of this thesis was proposed in the end.In the second chapter of this thesis, we have researched the reactions of aziridines with secondary amines which were catalysed by (n-Bu)3P. Firstly, we tried the ring opening reaction of N-tosylcyclohexeneimine aziridine with diethylamine by (n-Bu)3P in CH3CN under reflux, though the low yield (60%) and the long reaction time, we got target product. Then we optimized the reaction conditions, such as solvent, reaction temperature, and the ratios of reaction raw materials. When the mixture of CH3CN and H2O (V/V=10/1) was used as solvent, and the molar ratio of N-tosyl-cyclohexeneimine aziridine, diethylamine and (n-Bu)3P was1:2:0.15, we got better yield (83%). Finally, the scope of substrates of aziridine and secondary amine were investigated. All the reaction products were full characterized by IR, NMR. MS and EA. Compared with the reported methods for the preparation of1,2-diamino compounds, this procedure has the advantages such as simple operation, cheap catalyst, high yield and high regioselectivity.In the third chapter of this thesis, we studied the reaction of aziridines with hydrated nickel fluoride. Similarly, we tried the ring opening reaction of N-tosylcyclohexeneimine aziridine with NiF2·4H2O catalysed by (n-Bu)4NF, and got the expected product of β-fluoro amine. By further investigation of the reaction condition, we found the reaction preceeded soomthly in i-PrOH under reflux, and the preferential molar ratio of. N-tosyl-cyclohexeneimine aziridine, tetrabutyl ammonium fluorine and partly hydrated nickel fluoride (NiF2·4H2O was dried at120℃in vacuum to constant weight) was1:0.2:2. Finally, various aziridines were tested under preferential reaction conditions and corresponding β-amines were obtained. All the reaction products were full characterized by IR, NMR, EI-MS and EA.