Bis-8-hydroxyquinoline-armed diazatrithia-15-crown-5 and diazatrithia-16-crown-5 ligands: Possible fluorophoric metal ion sensors
Bis-8-hydroxyquinoline-armed diazatrithia-15-crown-5 and diazatrithia-16-crown-5 ligands: Possible fluorophoric metal ion sensors
复制标题
DOI：
10.1021/jo0017584
复制
发表时间：
2001-07-13
影响因子：
3.6
通讯作者：
Izatt, RM
中科院分区：
文献类型：
--
作者：
Bronson, RT;Bradshaw, JS;Izatt, RM
报道了一系列含两个8-羟基喹啉侧臂的二氮杂三硫杂-15-冠-5和二氮杂三硫杂-16-冠-5配体的合成和初步的物理化学性质。配体通过两步法制备。首先，通过用各种二硫醇处理双（α-氯代酰胺）5，然后用硼-THF络合物还原来制备二氮杂三硫代冠醚11和12。羟甲基取代的大环12在无水HCl中重排为羟基取代的二氮杂三硫杂-16-冠-5。通过曼尼希氨基甲基化反应将大环二胺11-13转化为5-氯-8-羟基喹啉-7-基甲基-取代的二氮杂三硫杂冠醚14-16，或通过使用8-羟基喹啉-2-甲醛还原胺化转化为8-羟基喹啉-2-基甲基-取代的二氮杂三硫杂冠醚17-19。初步的光物理研究表明，配体16和19在Zn ~（2+）存在下表现出增强的荧光，表明这些配体可以作为Zn ~（2+）的化学传感器。
The synthesis and preliminary photophysical properties of a series of diazatrithia-15-crown-5 and diazatrithia-16-crown-5 ligands containing two 8-hydroxyquinoline sidearms are reported. The ligands were prepared by a two-step process. First, diazatrithiacrown ethers 11 and 12 were prepared by treating bis(alpha -chloroamide)5 with various dimercaptans followed by reduction using a boron-THF complex. Hydroxymethyl-substituted macrocycle 12 was rearranged to hydroxysubstituted diazatrithia-16-crown-5 in refluxing aqueous HCl. Macrocyclic diamines 11-13 were converted to either 5-chloro-8-hydroxyquinolin-7-ylmethyl-sudstituted diazatrithiacrown ethers 14-16 by a Mannich aminomethylation reaction or to 8-hydroxyquinolin-2-ylmethyl-substituted diazatrithiacrown ethers 17-19 by reductive amination using 8-hydroxyquinoline-2-carboxaldehyde. Preliminary photophysical studies show that ligands 16 and 19 exhibit increased fluorescence in the presence of Zn2+, indicating that these ligands could be chemical sensors for Zn2+.