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将SO_4~(2-)型固体酸SO_4~(2-)/TiO_2的Lewis酸性位点与BINOL的Brnsted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。
The Lewis acidic sites of SO 4 2- type / TiO 2 solid acid and the Brnsted acidic sites of BINOL were loaded, and BINOL loaded SO 4 with strong double hydrogen bond donor was prepared ~ (2 -) / TiO_2 catalyst. Aromatic imines prepared by the condensation of aromatic substituted primary amines and cinnamic aldehydes with different substituents were used as catalytic substrates. Under the catalysis of 10 mol% BINOL supported SO 4 2- / TiO 2 catalysts, Alkyl ester (nucleophile) for phosphine hydrogenation. At the same time, by comparing the catalytic activity of SO_4 ~ (2 -) / TiO_2 supported by solid acid SO_4 ~ (2 -) / TiO_2, BINOL and BINOL, the SO_4 ~ (2 -) / TiO_2 catalyst supported by BINOL was objectively Evaluation. In addition, a-aminophosphonate derivatives were successfully synthesized with BINOL supported SO_4 ~ (2 -) / TiO_2 as catalyst under the optimal conditions. The yield of the α-amino phosphonates was 80% ~ 88%. In addition, based on the hydrogen bonding mode of action, a suitable mechanism for phosphine hydrogenation reaction is proposed.