以氨三乙酸为母体的三脚架型配体的合成

Preparation of Amide-Type Tripodal Ligand from Nitrilotriacetic Acid

为了提高酰胺型三脚架型配体的产率,进一步研究其与稀土离子的配位形式及配合物的荧光性能,以氨三乙酸为母体,草酰氯为氯化试剂,与4种胺在较温和的条件下合成了具有三脚架型结构的配体(L1—L4),并考察了实验条件、反应温度、反应体系溶剂、缚酸剂、反应时间及催化剂对反应产率的影响.结果表明,在无水条件下,氯化和胺化的反应温度分别不超过40℃和50℃,用少量的吡啶做缚酸剂,DMF做催化剂,溶剂为无水四氢呋喃,胺化反应10 h时产率较高.该实验条件温和,分离纯化简单,氯化和胺化反应产率大大提高,从而有利于对三脚架型配合物性质的研究.

To improve the yield of an Amide-type Tripodal Ligand and investigate its coordination with rare earth ion under mild condition, a series of Amide-type Tripodal Ligands（L1-L4 ） have been prepared by the reactions of nitrilotriacetic acid and oxalyl chloride with four kinds of amides,respectively. The influencing factors of experimental conditions including reaction temperature, solvent, reaction time, acid binding agent and catalyst have been investigated. The results showed that the optimal reaction conditions should be executed in THF for ten hours without water, at 40℃ and 50℃ of chlorination and amination using pyridine and DMF as acid binding agent and catalyst, respectively. The processes had some advantageous including mild experimental conditions, simple separation and good yield.