Complex Combinations of Some Transition Metals with New Unsymmetrical Porphirins

The biological and biomedical importance of the porphyrinic compounds have made them attractive target of study for many years. They are used in treatment of various diseases such as cancer therapy, treatment of psoriasis, viral and bacterial infections [1-19]. The therapeutic effect of porphyrins originates from their ability to preferentially accumulate in the diseased tissue and to photogenerate singlet oxygen or free radicals, species responsible for the cell inactivation. These reactive species can be produced through the interaction of porphyrinic compound with visible light and in the presence of molecular oxygen. Due of their luminescent properties, porphyrinic compounds are also used as fluorescent markers in detection of various cancer type [1-6, 20]. Although many metalloporphyrins have demonstrated versatility for both diagnosis and therapy, their poor intracellular localization justify further researches concerning increasing their tumor selectivity thereby increasing their ability to delineate tumor cells and protect healthy cells during photodynamic therapy. Taking into account the fact that nature substituents at the periphery of the tetrapyrrole macrocycles and the type of the metallic ion are responsible for localization at the cellular level [21, 22], in our research we synthesized metalloporphyrins with a slight amphoteric character which favours a better transfer at the cellular level, both in polar (the external environment of the cell) and nonpolar (the lipidic double layer of the cellular membrane) media [2329]. Another factor with direct influence on biomedical efficiency of the porphyrinic compounds is their purity degree, which is highly dependent on the route of the approached synthesis. As part of our ongoing research in the development of novel synthetic routes to the synthesis of new asymmetrical porphyrinic compounds by use of green chemistr y techniques, in this paper we describe, comparatively with the classical method, a convenient route for the direct synthesis of two unsymmetrical metalloporphyrins starting from substituted benzaldehydes, pyrrole, metallic salts and under solvent free conditions. Thus, Zn(II)-5-(2-hydroxyphenyl)-10,15,20–tris-(4-acetoxy3-methoxyphenyl)porphyrin (Zn(II)TMAPOHo) and Cu(II)5-(2-hydroxyphenyl)-10,15,20–tr is -(4-acetoxy-3methoxyphenyl)porphyrin (Cu(II)TMAPOHo) (fig. 1) were obtained under environmental and reproducible laboratory conditions, in a short time and with good yields. Complex Combinations of Some Transition Metals with New Unsymmetrical Porphirins