Derivatizable novel beta-tetra 7-oxycoumarin-3-carboxylate substituted metallophthalocyanines: Synthesis and characterization

Abstract

In this study, a novel phthalonitrile, ethyl 7-(3,4-dicyanophenoxy)coumarin-3-carboxylate (1), was prepared and characterized. The metallophthalocyanines (3-6) were prepared by cyclotetramerization of 1 with the corresponding metal salts [Zn(OAc)(2)center dot 2H(2)O, Co(OAc)(2)center dot 4H(2)O, Cu(OAc)(2), Ni(OAc)(2)center dot 4H(2)O] in 2-chloronaphthalene. Reaction of 3 with aqueous hydrochloric acid gave the coumarino-zincphthalocyanine (3a) carrying carboxyl groups at the 3-position of all the coumarin moieties. Treatment of compound 3a with aqueous NaOH/AgNO3 or aqueous NaOH in N,N-dimethylformamide (DMF) gave the expected silver (3c) or sodium (3d) salts, respectively. The four carboxylic groups in coumarino-zincphthalocyanine (3a) and the four carboxylate groups in 3d make the compounds have good solubility in water. Heating of the acyl chloride derivative of 3 with morpholine in DMF yielded the corresponding 3-carboxymorpholinamide (3b). The newly prepared compounds, phthalonitrile and metallophthalocyanines, have been characterized by FT-IR, UV-Vis, MALDI-TOF and H-1 NMR spectroscopies. (C) 2010 Elsevier Ltd. All rights reserved.