The Synthesis, Characterization, Applications Of Biscyclopentadiene Zirconium Bisperfluorooctanesulfonate

In recent years, with the synthesis of organic transitional metal compounds. A number of organic zirconium compounds serve as Lewis acid catalysts in Organic synthesis. Normally, their Lewis acid is too mild to form carbon-carbon bond, carbon-nitrogen bond, at the same time, some organic zirconium compounds sensitive to wa-ter, atmosphere, and drawbacks such as unstable, the harsh reaction condition. which to some extent, has hindered zirconium compounds more widely used. Hence, the increase of the Lewis acidity of organic zirconium compounds is of prime importance to expand the scope of their synthetic utility. Otera reported that perfluor ooctanesulfonate metal compounds are the air-stable and water-stable compounds, Perfluoroalkylsulfonate is an electron-withdrawing group, it can effectively increase the acidity of zirconium compounds. And it's reported that trifluoromethylsulfonic metal compounds can catalyze carbon-carbon bond-forming reactions effectively. However their hygroscopic nature did not allow us to fully characterize the structure of these compounds. In this paper, we synthesize and characterize biscyclopentadiene zirconium bisperfluorooctanesulfonate compound, furthermore, its catalytic activity is assessed in the organic synthesis. The contents of the paper include five parts:(1) Biscyclopentadiene zirconium bisperfluorooctanesulfonate was synthesized using AgOSO2C8F17 and Cp2ZrCl2,the yield of which is up to 85%. The product was analysized by 1H NMR and 19F NMR, and the solubility in organic solvent, as well as the stability of which was studied in air and water.(2) The catalytic activity of biscyclopentadiene zirconium bisperfluorooctanesulf onate was assessed in Mannich reaction. The Mannich reaction is one of the most usef ul reactions for the synthesis of nitrogen-containing compounds and is an effective method for the construction of carbon-carbon bond. In this paper, the reaction of acet ophenone with aromatic aldehydes and aromatic amines by biscyclopentadiene zirco nium bisperfluorooctanesulfonate as catalyst at room temperature, and solvent-free,a series ofβ-amino ketones were synthesized. The products were easy separated from catalyst and the yield of which is up to 95%.(3) The catalytic activity of biscyclopentadiene zirconium bisperfluorooctanes ulfonate was assessed in Mukaiyama-Aldol reaction. A series of aromatic alcohol compounds were synthesized at room temperature. The products were easy separated from catalyst and the yield of which is up to 92%. (4) The catalytic activity of biscyclopentadiene zirconium bisperfluorooctanes-ulfonate was assessed in esterification. It's found that the catalyst can induce the reaction of aromatic alcohol and acetic anhydride rapidly at room temperature,but induce the reaction of long-fatty alcohol and acetic anhydride at higher temperature. According to track response by TLC,the yield of the reaction is up to 90%.(5) The catalytic activity of biscyclopentadiene zirconium bisperfluorooctanes ulfonate was assessed in allylation. By the reaction of aromatic aldehyde and tetraallylstannane, a series of unsaturated aromatic alcohol were synthesized,which are the important intermediate of Organic Synthesis. In this paper,the reaction of aromatic aldehyde and tetraallylstannane by biscyclopentadiene zirconium bisperfluorooctanes ulfonate as catalyst at room temperature, the yield of which is up to 90%. Meanwhile, the amount of the catalyst was studied.