Synthesis of β-Substituted Tetramethyltetraazacyclotetradecatetraene and Its Metal(II) Complexes

Article abstract of DOI:10.1246/bcsj.54.2348

N,N'-Bis(1-methyl-3-thioxo-1-butenyl)ethylenediamine (3) was prepared by reaction of N,N'-bis(1-methyl-3-oxo-1-butenyl)ethylenediamine with phosphorus pentasulfide in pyridine.The reaction of 3 with ethylenediamine gave 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradecaa-4,6,11,13-tetraene (4) in a 46percent yield.The reactivity of the β-positions of 4 and its metal(II) complexes (M = Cu, Ni, Pd) toward various electrophilic reagents was explored, and some β,β'-bissubstituted tetraaza macrocyclic compounds (substituents = Cl, SC6H4NO2(o), N2Ph) and their metal complexes were prepared, respectively.The former also reacted with metal(II) acetates to afford the same metal complexes.