Macrocyclic Metal Complex, [6,15-Dimethyl-5,8, 9,14,17,18-hexaazadibenzo[a, A]cyclotetradecene]nickeI(II) and It's Mono- and Disulfonic Acid Derivatives

The templet condensation of N-acetonylidene-N′-(o-aminophenyl)hydrazine (o-NH₂C₆H₄ NHN=CHCOCH₈) in the presence of nickel acetate in the mixed solvent of pyridine and ethanol (1: 10) yielded a new macrocyclic nickel complex([6,15-dimethyl-5, 8, 9,14,17,18-hexa-azadibenzo[a, A]cyclotetradecene]nickel(]I)) [2]. Central nickel of [2] could not be removed by following the treatments which were employed for the demetalation of the tetraaza-analogue of [2] ([6, 8,15,17-tetramethyl-5, 9,14,18-tetraazadibenzo[a,A]cyclotetradecene]niekel(E)): (i) suspending [2] in 1% HCl-ethanol and (ii) dissolving [2] in cone, sulfuric acid. Sul-fonation of [2] in cone, sulfuric acid and in 20% oleum afforded mono-[2a] and disulfonic acid[2b], respectively. [2a] and [2b] dyed fibers of wool, silk, and nylon dark green shade. The fastnesses of the dyeings against washing and light were 5 and 2∼3, respectively.