The Synthesis of New Phthalocyanines Substituted with 12-Membered Diazadioxa Macrocycles

 A macrocyclic diazadioxa dibromo compound was synthesized by ring closure of 1,2-bis-(2-iodoethoxy)-4,5-dibromo-benzene and 1,4-bis-(p-tolylsulfonyl)-ethylenediamine. Its phthalonitrile derivative was obtained by cyano substitution. This diazadioxa macrocyclic dibromo derivative was directly converted into the copper(II) phthalocyanine by reaction with CuCN in tetramethyl urea. Conversion of this phthalonitrile derivative into the metal-free phthalocyanine was accomplished by refluxing with DBU. The zinc(II) phthalocyanine was prepared by reaction of the dinitrile derivative with Zn(OAc)₂ in quinoline. The lutetium bis-(phthalocyaninate) complex was obtained by treating the dinitrile derivative with anhydrous lutetium acetate and DBU in 1-hexanol. The new compounds were characterized by elemental analyses and IR, ¹H NMR, mass, UV/Vis, and ESR spectra.