Lipophilic Cage Ligands Containing Two Tightly Connected 1,7-Dioxa-4,10-diazacyclododecane Rings: Synthesis and X-ray Structure of a Sodium Perchlorate Complex

Article abstract of DOI:10.1021/jo00257a016

Sodium perchlorate complexes 2 of lipophilic macrotricyclic receptors 1 were obtained in high yield by following a synthetic route in which sodium cation acts as the templating agent in the last step.Complexes with several inorganic salts were directly prepared from the free ligands 1, obtained by decomplexation of 2, or via anionic exchange from the complexes 2.Extraction data of alkali halides under two-phase conditions (H2O-CHCl3) with ligand 1a showed a cation extraction selectivity order Na⁺ >> K⁺ > Li⁺.Under liquid-liquid two-phase conditions, ligands 1 proved to be effective phase-transfer catalysts in hydroxide ion initiated carbanion formation from very weak carbon acids.The sodium complex 2a was crystallographically characterized.The sodium cation is in a nonsymmetric cubic environment of four oxygen (Na <*> O 2.46 Angstroem) and four nitrogen (Na <*> N 2.79 Angstroem) atoms.