Highly active and green aminopropyl-immobilized phosphotungstic acid on mesocellular silica foam for the O-heterocyclization of cycloocta-1,5-diene with aqueous H2O2
作者:Ruihua Gao、Quanjing Zhu、Wei-Lin Dai、Kangnian Fan
DOI:10.1039/c0gc00691b
日期:——
The heteropoly phosphotungstic acid, H3PW12O40 (HPW), was successfully immobilized on the surface of MCF, SBA-15 and MCM-41 by means of chemical bonding to aminosilane groups. The as-obtained materials were characterized by N2 sorption, TEM, XRD, FT-IR, 13C-, 29Si-, 31P-MAS NMR and XPS. Characterization results suggest that the surface area decreased after grafting amino groups to silica. The as-prepared HPW-NH2-MCF is highly efficient in the O-heterocyclization of cycloocta-1,5-diene (COD) to 2,6-dihydroxy-9-oxabicyclo[3.3.1] nonane (1) and 2-hydroxy-9-oxabicyclo [3.3.1] nonane-6-one (2) with a COD conversion of 100% and (1 + 2) selectivity up to 98%. It is worth mentioning that this material could be reused six times without any significant loss of activity and selectivity. The good stability can be attributed to the strong interaction between the amino groups on the surface of MCF and HPW anions.
通过化学键合氨基硅烷基团,异多聚磷钨酸(H3PW12O40,HPW)成功固定在MCF、SBA-15和MCM-41的表面。通过N2吸附、TEM、XRD、FT-IR、13C-、29Si-、31P-MAS NMR和XPS对所得材料进行表征。表征结果表明,在硅石上接枝氨基后,表面积减小。制备的HPW-NH2-MCF在环辛烷-1,5-二烯(COD)的O-杂环化反应中非常有效,可将COD转化为2,6-二羟基-9-氧杂双环[3.3.1]壬烷(1)和2-羟基-9-氧杂双环[3.3.1]壬烷-6-酮(2),COD转化率为100%,(1+2)选择性高达98%。值得一提的是,这种材料可以重复使用六次,而活性与选择性不会明显降低。这种良好的稳定性可归因于MCF表面氨基与HPW阴离子之间的强相互作用。