【作者】 刘尚义； 张召举； 于青； 王忠卫；

【Author】 Shangyi Liu;Zhaoju Zhang;Qing Yu;Zhongwei Wang;College of Material Science and Technology,Shandong University of Science and Technology,579 Qianwangang Road Economic & Technical Development Zone,Qingdao Shandong Province;

【机构】 山东科技大学材料科学与工程学院；

【摘要】 苯与PCl3在无水AlCl3作用下发生Friedel-Crafts反应,是合成苯基二氯化膦(BPD)的一种传统方法,由于反应中BPD与AlCl3络合物的生成使BPD不能直接蒸馏分离,造成BPD的合成存在严重污染问题。课题组较早探索了室温离子液体(ILs)催化苯与PCl3反应的绿色工艺,实现了BPD的直接分离,该工艺已实现工业化。本文通过NMR手段研究了[Et3NH]-AlCl3 ILs催化苯与PCl3的反应机理,确定体系中AlCl3是主要催化活性物,AlCl3在PCl3层中参与反应与BPD生成络合物,该络合物又在ILs层中与[AlCl4]-作用使BPD解离。AlCl3、BPD、BPD络合物在PCl3和ILs层中的溶解性及ILs层中存的平衡对BPD以游离分子形式存在起了重要作用。更多还原

【Abstract】 The Friedel-Crafts reaction of benzene and PCl3 catalyzed by AlCl3 is the classical method to synthesize benzenephosphorus dichloride(BPD), BPD and AlCl3 will form complex during the reaction, which make the isolation of BPD difficult and dirty. We have found that room temperature ionic liquids(ILs) can catalyze the same reaction and the BPD can be isolated by direct distillation. This technique has been industrialized. This work is to study the Friedel-Crafts reaction mechanism of benzene and PCl3 catalyzed by [Et3NH]-AlCl3 ILs through NMR analysis method. It was found that, AlCl3 in the ILs is the active catalyst, and it will also form complex with BPD during the reaction. The complex then participate in the reaction with [AlCl4]- to make BPD free. The the solubility of BPD, AlCl3 and complex in PCl3 and ILs, together with the balances in the ILs play important roles to make the BPD free druing the reaction.更多还原