合成二茂钛衍生物的超分子界面催化反应研究  

Preparation of Titanocene Derivatives by Interfacial Supramolecular Catalytic Reactions

作　　者：高子伟[1] 孙平[1] 高玲香[1] 韩丽[1] 袁文权[1] 刘宇[1] 张军锋[1] 吕敏[1] 

机构地区：[1]陕西师范大学化学与材料科学学院化学系,西安710062

出　　处：《化学学报》2004年第10期979-985,共7页Acta Chimica Sinica

基　　金：国家自然科学基金 (No.2 0 1 0 1 0 0 5);陕西省自然科学基金 (No .2 0 0 3B0 4 );陕西师范大学校重点资助项目

摘　　要：设计了一种超分子催化合成二茂钛衍生物的反应模型 ,并通过水溶性 β 环糊精聚合物 (WS β CDP)催化两相法合成二茂钛衍生物的反应得到了证实 .利用荧光光谱和电子吸收光谱对反应过程进行了在线监测 ,发现WS β CDP可作为超分子微反应器 ,优先与配体可逆地形成超分子配合物 ,将配体激活 ,并在两相界面与二氯二茂钛发生反应 ,形成目标产物 ;之后 ,产物脱离空腔留在了有机相 ,而下一个配体则进入反应器继续反应 .同时发现 ,体系中WS β CDP的存在对提高二茂钛物种的稳定性非常有利 ,并使其安全pH值提高至 10 60 .Based on the concept of enhancing the ability of forming complex of ligand, a new approach for synthesizing titanocene derivatives catalyzed by supermolecule is presented herein. The feasibility of this approach was demonstrated using the reaction of forming titanocene derivatives in two phase (H2O/CHCl3) system catalyzed by water soluble beta-cyclodextrin polymer (WS-beta-CDP). Based on the electronic absorption and fluorescence spectra, it was found that when beta-CDP is present as a microreactor in the reaction system, it selects ligand firstly in the aqueous phase to form a supramolecular complex, making ligand more active and react interfacially with titanocene dichloride in the organic phase more easily to form titanocene complex. Then, the next ligand substitutes for the titanocene complex and enter the microreactor, thus making the reaction to continue. At the same time, it was found that WS-beta-CDP can enhance the stability of the species of titanocene ('Cp2Ti') and form titanocene complexes at pH = 10.60.

关 键 词：二茂钛衍生物 超分子界面 催化反应 配位能力 水杨酸 肿瘤 

分 类 号：O643.3[理学—物理化学]