SO_4^(2-)/TiO_2固体酸负载BINOL催化膦氢化反应  

BINOL-Loaded SO_4^(2-)/TiO_2 Solid Acid Applied to Hydrophosphonylation

作　　者：宋友德[1,2] 姚元勇[1] 舒华[1] 

机构地区：[1]铜仁学院应用化学研究所材料与化学工程学院,贵州铜仁554300 [2]铜仁广播电视大学,贵州铜仁554300

出　　处：《化学试剂》2017年第7期759-764,共6页Chemical Reagents

基　　金：贵州省教育厅自然科学"青年"基金资助项目(KY.(2014)317);贵州省教育厅自然科学基金资助项目(KY.(2012)069)

摘　　要：将SO_4^(2-)型固体酸SO_4^(2-)/TiO_2的Lewis酸性位点与BINOL的Brnsted酸性位点进行负载,制备出具有较强双氢键供体的BINOL负载的SO_4^(2-)/TiO_2催化剂。以不同取代基团的芳香族伯胺和肉桂醛缩合制备的芳香族亚胺为催化底物,在10 mol%BINOL负载的SO_4^(2-)/TiO_2催化剂的催化作用下,与亚磷酸二烷基酯(亲核试剂)进行膦氢化反应。同时,通过对比固体酸SO_4^(2-)/TiO_2、BINOL、BINOL负载的SO_4^(2-)/TiO_2催化剂的催化活性,从而对BINOL负载的SO_4^(2-)/TiO_2催化剂进行客观地评价。另外,在较优的催化条件下,以BINOL负载的SO_4^(2-)/TiO_2为催化剂,成功地合成了α-氨基膦酸酯类衍生物,且产率可达80%~88%。另外,基于氢键的作用模式,提出了适合于膦氢化反应较为合理的作用机理。By loading of solid acid SO4^2-/TiO2 with Lewis acidic sites onto BINOL with Brnsted acidic sites,the potent catalyst BINOL-loaded SO4^2-/TiO2 with much potential double H-bonding donors have been prepared.The catalytic substrate of aromatic imines prepared by the condensation of diverse substitutes aromatic primary amine with cinnamylaldehyde was permitted to proceed hydrophosphonylation with dialkyl phosphate as nucleophile in the presence of solid acid BINOL-loaded SO4^2-/TiO2（10mol%）.Under the optimal conditions,the BINOL-loaded SO4^2-/TiO2 acted as valid catalyst was successfully utilized to afford α-aminophosphonate derivatives,in yields of 80% - 88%.Simultaneously,as comparing BINOL-loaded SO4^2-/TiO2 with SO4^2-/TiO2 and BINOL in catalytic activity,BINOL-loaded SO4^2-/TiO2 catalyst was objectively obtained assessment.In addition,relying on hydrogen-bonding interactions,the mechanism has been proposed for BINOL-loaded SO4^2-/TiO2.

关 键 词：固体酸 BINOL负载的SO42-/TiO2 Α-氨基膦酸酯 膦氢化反应 

分 类 号：O621.3[理学—有机化学]