高分子无机锡配合物催化环己酮Baeyer—Villiger氧化性能研究

将聚酰胺一胺树状分子的一到三代通过固相合成担载于纤维素上，分别用2，4-二羟基苯甲醛和邻羟基苯甲醛对其外围的氨基进行了修饰，再与SnCl2·2H2O反应形成两类树状大分子金属锡配合物．用ICP、IR和XPS对此类配合物的结构进行了表征．将此类配合物用于30％双氧水氧化环己酮的Baeyer-Villiger（B-V）反应的非均相催化剂，研究表明，在此类配合物作用下，环己酮高选择性地转化为ε-己内酯．比较不同配体修饰的催化剂作用下的氧化反应情况，发现配体对金属的担载量和催化活性均有不同程度的影响．此类催化剂以天然高分子纤维素为载体，具有原料来源丰富、制备方法简单、催化反应时间短、可重复利用等特点．

Catalytic Properties of Macromolecular Inorganic Sn Complexes for Baeyer-Villiger Oxidation of Cyclohexanone

Cellulose supported Different generations polyamidoamine dendrimers were prepared by solid phase synthesis methodology, the peripheral amino groups on PAMAM have been modified by 2,4-dihydroxybenzaldehyde and salicylaldehyde, then the ligands reacted with SnCl2 · 2H2O to obtained cellulose supported dendritic Sn complexes. The ligands and the complexes were well characterized by ICP, IR and XPS. The Baeyer-Villiger oxidation of eyclohexanone to the corresponding lactones were catalyzed by cellulose-supported dendritic Sn complexes in the presence of environmentally friendly 30 hydrogen peroxide, it was shown that all the complexes with different generations exhibit promis- ing catalytic activities for the oxidation of cyclohexanone under the mild condition, The effects of the ligand to catalytic acitivity of cmplex had also been studied, it was discovered that the ligand played a vital role in metal loadings and the catalytic activity of the complexes. The catalysts could be obtained in a simple and efficient manner using natural product cellulose as the supporter. Moreover, the catalysts were very convenient for separation from the reaction mixture after the completion of the oxidation and can be recycled.