Syntheses of diazadithiacrown ethers containing two 8-hydroxyquinoline side arms

Ten new diazadithiacrown ethers containing two 8-hydroxyquinoline (HQ) side arms attached through the HQ 7-positions and four new diazadithiacrown ethe rs containing two HQ sidearms attached through the HQ 2-positions have been prepared. Some of these new ligands also contain a hydroxymethyl substitue nt. The starting macrocyclic diazadithiacrown ethers were obtained by treat ment of a bis(a-chloroamide) with the appropriate dimercaptan using K2CO3 a s the base followed by reduction of the resulting macrocyclic dithiadiamide by BH3-THF or by NaBH4 in the presence of BF3-ether as a catalyst. HQ-cont aining ligands 23-32 were synthesized by a Mannich reaction of the secondar y macrocyclic diamines with the substituted-8-hydroxyquinoline. HQ-containi ng ligands 33-36 were prepared by reductive amination of the secondary macr ocyclic diamines with 8-hydroxyquinoline-2-carbaldehyde. The HQ-containing diazadithiacrown ethers which also contain a hydroxymethyl group on the mac roring (23-29, 33, and 35) are more soluble in polar solvents than those wi thout the hydroxymethyl group.