Triphenyl Bismuth Bisperfluorooctanesulfonate Complex And Its Application In The Synthesis Of Nitrogen-containing Compounds

Bismuth has attacted much attention since its non-toxic, non-radioactive and bismuth complexes specific activity. Recently, a series of organic bismuth complexes with diverse structure and special performance has been synthesized and applied in various organic reactions as reagents or catalyst. However, due to the unstable bismuth-carbon bond and air-sensitive features as well as lower catalytic efficiency, the application of organobismuth complexes as catalyst in organic synthesis is still limited. Accodingly to literatures, incorporation of triflic acid to the metal atom, the catalytic activity of organobismuth complexes can be enhanced, but the air-moisture property is still remaining. Based on our previous work, the long-chain perfluorooctane sulfonic acid with strong electron-withdrawing ability is introduced, the air-stable organobismuth complexes is obtained. Meanwhile, due to the presence of electron withdrawing group, the Lewis acidity is also increased obvirously. In this thesis, we synthesized triphenyl bismuth bisperfluorooctanesulfonates complex and characterized its structure through NMR, ESI-MS, TG-DSC, IR, etc. Also we assess its catalytic activitiy for synthesis of Nitrogen-containing compounds. The main results are as follows:(1) Triphenyl bismuth bisperfluorooctanesulfonates complex is synthesized by treatment of triphenylbismuth dichloride with silver perfluorooctanesulfonate in 82% yield, and analysized by 1H NMR, 1 9F NMR, ESI-MS and IR, etc. Also the thermostability of which is analysized by TG-DSC curves, the results show the complex is air-stable and thermos-stable under 180 oC. Its Lewis acidity is 3.3?Ho?4.8, and the complex can be used as Lewis acid catalyst.(2) The catalytic activity of t riphenyl bismuth bisperfluorooctanesulfonates complex is assessed for the synthesis of diindolylmethane derivatives with high activity and recyclability in good to excellent yields in mild condition. The catalyst can be reused for six times without any activity loss.(3) The catalytic activity of triphenyl bismuth bisperfluorooctanesulfonates complexes was assessed in the Biginelli reaction of aldehydes with 1,3-dicarbonyl compound and urea. A series of dihydropyrimidinones were synthesized in good to excellent yields, up to 95%. And no anhydrous solvent and inert gas is required in the procedure.(4) The catalytic activity of t riphenyl bismuth bisperfluorooctanesulfonates complexes was assessed in the reaction of aldehydes with 1,3-dicarbonyl compound and Ammonium acetate. A series of dihydropyridines were synthesized with high efficiency, the yield is up to 90%.(5) The catalytic activity of t riphenyl bismuth bisperfluorooctanesulfonates complexes was assessed in the reaction of amine with epoxide compound. A series of ?-amino alcohols was synthesized under solvent-free condition in good to excellent yields.In this thesis, triphenyl bismuth bisperfluorooctanesulfonates is designed and synthesized as air-stable and water-tolerate Lewis acid catalyst for C-C and C-N bond formation for the synthesis of Nitrogen-containing compounds with high efficiency under mild condition, no strictly anhydrous and oxygen-free environment is required. Furthermore, the catalyst can be recycled for at least four times without catalytic activity loss.