全氟辛基磺酸稀土金属盐催化氟两相Friedel-Crafts烷基化反应

Friedel-Crafts Alkylation in Fluorous Biphasic System Catalyzed by Rare Earth(Ⅲ) Perfluorooctanesulfonates

制备了全氟辛基磺酸稀土金属盐[RE(OSO2C8C17)3,RE:Sc,Y,La^Lu],并研究了将其作为催化剂催化氟两相烷基化反应。全氟己烷(C6F14)、全氟甲苯(C7F8)、全氟甲基环己烷(C7F14)、全氟辛烷(C8F18)、1-溴代全氟辛烷(C8F17B r)和全氟萘烷(C10F18,顺式与反式的混合物)可作为该反应的氟溶剂。考察了带有不同配体的稀土金属催化剂对反应的影响。研究表明,Yb(OSO2C8F17)3和C10F18分别是最好的氟代催化剂和氟溶剂。以Yb(OSO2C8F17)3为催化剂在C10F18中苯甲醚和苯甲醇的烷基化反应得率为96%。含有催化剂的氟相通过简单的相分离,可回收利用。氟相重复使用5次,其催化活性降低不大。

The rare earth （ Ⅲ ） perfluorooctanesulfonates （ RE （ OSO2C8F17 ） 3, RE ： Sc, Y, La ～ Lu ） catalysts have been prepared and used in Ffiedel-Crafts alkylation in fluorous biphasic systems. Perfluorohexane （ C6 F14 ）, perfluoromethylcyclohexane （ C7 F14 ）, perfluorotoluen （ C7 F8 ）, perfluorooctane （ C8 F17 ）, perfluorooctyl bromide（ CsF17Br） and perfluorodecalin（ C10F18, cis and trans-mixture） can be used as the fluorous solvent for this kind of reaction. The catalytic activities of other rare earth metal salts with different ligands were tested. The results show that Yb（ OSO2C8F17）3 and C10F18 were the best catalyst and fluorous solvent respectively. The yield of alkylation of anisole with benzyl alcohol was 96% in the presence of Yb（ OSO2C8F17 ）3 and C10F18. By simple phase-separation the fluorous phase containing only catalyst could be re-utilized up to five timies with a slight decrease in activity.