Bis-8-hydroxyquinoline-Armed Diazatrithia-15-crown-5 and Diazatrithia-16-crown-5 Ligands: Possible Fluorophoric Metal Ion Sensors

Abstract

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 hydroxy-substituted diazatrithia-16-crown-5 in refluxing aqueous HCl. Macrocyclic diamines 11-13 were converted to either 5-chloro-8-hydroxyquinolin-7-ylmethyl-substituted 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 Zn(2+), indicating that these ligands could be chemical sensors for Zn(2+).