Phthalocyanines and related compounds: XLIII. Synthesis of poly[phenyl(alkyl)sulfanyl]-substituted phthalonitriles and some phthalocyanines based thereon

Abstract

Nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by benzene- and alkanethiols in the presence of a base was studied at different reactant ratios. The substitution is characterized by complete regioselectivity: the chlorine atom in position 4 of tetrachlorophthalonitrile is replaced first; next follows replacement of the 5-chlorine atom. The reactions of tetrachlorophthalonitrile with nucleophiles at ratios of 1:2 and 1:4 lead to the formation of the corresponding 3,6-dichloro-4,5-bis[phenyl(alkyl)sulfanyl]- and tetrakis[phenyl(alkyl)sulfanyl]phthalonitriles. The latter were converted into metal complexes of [phenyl-(alkyl)sulfanyl]-substituted phthalocyanines which absorb in the red and near-IR regions of the electronic spectra.