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

N,N′-Bis(1-methyl-3-thioxo-1-butenyl)ethylenediamine (3) was prepared by the 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-tetraazacyclotetradeca-4,6,11,13-tetraene (4) in a 46% 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 (substituent=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.