MMT/FeCl3催化的α-羰基二硫缩烯酮与二苯甲醇的Friedel-Crafts烷基化反应

摘要

研究了MMT/FeCl3催化α-羰基二硫缩烯酮与二苯甲醇的Friedel-Crafts烷基化反应,合成了22个二硫缩烯酮类化合物(3a~3v),其中3b, 3d~3f, 3h~3r和3t为新化合物,其结构经1H NMR和13C NMR表征.以3a的合成为例,对反应条件进行优化.结果表明:在最优反应条件[1-(1,3-二噻烷-2-亚甲基)-4-苯基-3-丁烯-2-酮(1a) 0.25 mmol,二苯甲醇0.3 mmol, MMT/FeCl3 15 mmol%, CH2Cl2 2 mL,回流反应2 h]下,3a产率93%;MMT/FeCl3循环使用3次,收率基本维持不变.%Friedel-Crafts alkylation of α-oxo ketene dithioacetals with diphenylmethanols catalyzed by MMT/FeCl3 was developed.The reaction was efficiently performed in the presence of MMT/FeCl3(15 mmol%) at reflux for 2 h in CH2Cl2, affording twenty-two broader α-oxo ketene dithioacetals(3a~3v) in excellent yields.Among them, 3b, 3d~3f, 3h~3r and 3t were new compounds.The structures were characterized by 1H NMR and 13C NMR.Reaction conditions on yield of 3a were screened.The results indicated that yield of 3a was 93% under the optimized conditions[1-(1,3-dithiolan-2-ylidene)-4-phenylbut-3-en-2-one(1a) 0.25 mmol, diphenylmethanol 0.3 mmol, MMT/FeCl3 15 mmol%, CH2Cl2 2 mL, reaction at reflux for 2 h].The yield of 3a remain stable after MMT/FeCl3 recycling for three times.