Synthesis of diazadi(and tri)thiacrown ethers containing two 5-substituent(or 2-methyl)-8-hydroxyquinoline side arms

Sixteen new diazadi(or tri)thiacrown ethers containing two 5-substituent(or 2-methyl)-8-hydroxyquinolin-2-ylmethyl side arms have been prepared by a t hree-step process. First, the appropriate bis(alpha -chloroamide)s were tre ated with five dimercaptans in base to form macrocyclic di(or tri)thiadiami des. The macrocyclic diamides were reduced by BH3-THF to form 1,7-diaza-4-o xa-10,13-dithia-cyclopentadecane (11); 1,7-diaza-4,13-dioxa-10,16-dithiacyc looctadecane (12); 1,7-diaza-4-oxa-10, 13,16-trithiacyclooctadecane (13); 1 ,7-diaza-4,13,16-trioxa-10,19-dithiacycloheneicosane (14); and 1,10diaza-4, 7-dioxa-13,16-dithiacyclooctadecane (15). The diazadi(or tri)thiacrown ethe rs were then treated with 8-hydroxyquinoline, 8-hydroxy-5methylquinoline, 5 -chloro-8-hydroxyquinoline, and 8-hydroxy quinal dine in the presence of pa raformaldelyde in refluxing benzene to form the bis(8-hydroxy-5-substituent (or 2-methyl)quinolin-7-ymethyl)-substituted diazadi(or tri)thiacrown ether s 16-31. The crown ethers containing two 8-hydroxyquinoline or 8-hydroxyqui naldine side arms proved to be mixtures of about 90% bis(8-hydroxyquinolin- 7-ylmethyl)-substituted crown ethers; 9% mixed (8-hydroxyquinolin-7-ymethyl )-substituted and (8-hydroxyquinolin-5-ylmethyl)-substituted crown ethers; and 1% bis(S-hydroxyquinolin-5-ylmethyl)-substituted crown ethers.