Syntheses of diazadithiacrown ethers containing two 8-hydroxyquinoline side arms

Abstract

This paper is dedicated to Professor Miha AbstractTen new diazadithiacrown ethers containing two 8-hydroxyquinoline (HQ) sidearms attached through the HQ 7-positions and four new diazadithiacrown ethers containing two HQ sidearms attached through the HQ 2-positions have been prepared. Some of these new ligands also contain a hydroxymethyl substituent. The starting macrocyclic diazadithiacrown ethers were obtained by treatment of a bis(α-chloroamide) with the appropriate dimercaptan using K 2 CO 3 as the base followed by reduction of the resulting macrocyclic dithiadiamide by BH 3 -THF or by NaBH 4 in the presence of BF 3 -ether as a catalyst. HQ-containing ligands 23-32 were synthesized by a Mannich reaction of the secondary macrocyclic diamines with the substituted-8-hydroxyquinoline. HQ-containing ligands 33-36 were prepared by reductive amination of the secondary macrocyclic diamines with 8-hydroxyquinoline-2-carbaldehyde. The HQ-containing diazadithiacrown ethers which also contain a hydroxymethyl group on the macroring 23-29, 33, and 35 are more soluble in polar solvents than those without the hydroxymethyl group.

Synthesis of Bioactive Aminomethylated 8-Hydroxyquinolines via the Modified Mannich Reaction

“…Farruggia et al used microwave irradiation (600 W for 2-4 h) to optimise the preparation of 243e-l and efficiently carried out the syntheses in both toluene and 1,4-dioxane[165]. In addition to compounds described previously, 244a-d, 245a-c, and 245e-i were furnished by Bradshaw et al[161], 244e-g and 245d by Song et al[143,162] and 245j by Bronson et al[163].Scheme 19. Reaction of 8HQ and substituted 8HQs, CH2O and diaza-crown ethers.…”