Synthesis of dichloro phthalocyanine complexes of titanium, zirconium, and hafnium

New methods for preparation of high-pure titanium, zirconium and hafnium dichloride complexes of phthalocyanines are given, as well as their tolerance for hydrolysis is studied. The compounds were characterized by IR- and electron absorption spectra, test for the metal was made by titrimetric titration. Two ways of synthesis are developed: 1) equimolar amount of 2-methylnaphthalene, which chlorination products remove from the reaction mixture easily, is introduced in the reaction medium, 2) high-boiling alcohols are used as solvents. It is established that the introduction of 2-methylnaphthalene in the reaction mixture prevents chlorination of macrocycle during the process. It was noted that the hydrolysis of the conforming dichlorides instead of direct synthesis was preferential for the preparation of the pure titanium, zirconium and hafnium oxoforms of phthalocyanines