SYNTHESES OF MACROCYCLIC DIAMIDES AND TET RAAMIDES AND THEIR BINDING ABILITY WITH TRANSITION-METAL IONS

Four macrocyclic polyamides, ,29,30-octaazatricyclo[23.3.1.1(11,15)]tr iaconta-1 (29),11,13,15 (30),25,27-hexaene-2,10,16,24-tetrone (L1), 4- octyl-1,4,7-triazacyclotridecane-8,13-dione (L2), ylmethyl)-1,4,7,10-t etraazacyclododecane-2,6-dione (L3) and ridylmethyl)-1,4,7-triazacyclo tridecane-8,13-dione (L4) have been synthesized and the composition of the complex and the extraction equilibrium constants log K(ex) have b een determined by solvent extraction for some transition metal ions (C u2+, Co2+, Ni2+, Zn2+). These ligands formed the cationic complexes as 1 : 2 (L1 : Cu2+) and 1 : 1 (L2 and L3 ; Cu2+), and extracted Cu2+ se lectively from an equeous solution in the presence of picrate ion into 1,2-dichloroethane. Values log K(ex) for the cationic complexes of Cu 2+ with each ligand were increased in the order L1 < L2 < L3. In patic ular, L3 possessing a pyridine ring appendage of cooperative binding e xtracted Cu2+ effectively even in a strong acidic equeous solution, an d extracted Co2+, Ni2+, Zn2+ with same extent to Cu2+ from a singl met al solution, however predominantly extracted only Cu2+ in the competit ive extraction of these ions and Cu2+. L1 and L2 have little binding a bility for Co2+, Ni2+ and Zn2 + ions. L4 was soluble to some extent in the equeous phase, thus it is not appropriate as a ligand of solvent extraction.