Syntheses of novel unsymmetrically tetrasubstituted phthalocyaninato vanadyl and zinc complexes with a nitro or amino group

Four new unsymmetrical metallophthaiocyanines were synthesized. The vanadium trichloride-mediated statistical condensation of 5-nitro-1,3-diiminoisoindoline with 5-tert-butyl-1,3-diiminoisoindoline or with 5-neopentoxy-1,3-diiminoisoindoline in anhydrous 2-(N,N-dimethylamino)ethanol under reflux did not yield the desired 2-nitro-9,16,23-tri(tert-butyl)phthalocyaninato or 2-nitro-9,16,23-tri(neopentoxy)phthalocyaninato vanadyl complexes. but yielded the unexpected 2-amino-9,16,23-tri(tert-butyl)phthalocyaninato or 2-amino-9,16,23-tri(neopentoxy)phthalocyaninato vanadyl complexes. 2-Nitro-9,16,23-tri(tert-butyl) phthalocyaninato vanadyl complex was prepared by a statistical condensation of 4-tert-butylphthalonitrile and 4-nitrophthalonitrile in the presence of vanadium trichloride and dry urea at 175-180 degreesC,while zinc 2-nitro-9,16 23-tri(neopentoxy)phthalocyaninate was synthesized by the zinc acetate-mediated statistical condensation of the two corresponding 1,3-diiminoisoindolines in 2-(N.,V-dimethylamino)ethanol under reflux. All the target unsymmetrical phthalocyanines were separated by common column chromatography and characterized by elemental analysis., IR and H-1-NMR. UV-visible and fast-atom-bombardment mass spectroscopies. (C) 2002 Elsevier Science Ltd. All rights reserved.