Synthesis of unsymmetrically substituted subphthalocyanines

A series of new unsymmetrically substituted subphthalocyanines containing iodo or octylthioether substituents on the outer aromatic rings have been synthesized. The statistical reaction of one equivalent of 1,2-dicyano-3-iodobenzene whether with two equivalents of 1,2-dicyano-4-octylthiobenzene or with two equivalents of 1,2dicyano-4,5-dioctylthiobenzene in the presence of boron trichloride in 1-chloronaphthalene yielded in both cases all the possible expected unsymmetrically substituted subphthalocyanines, which were separated by column chromatography on silica gel. All compounds were identified by FAB mass spectrometry and then characterized by HR-LSIMS spectrometry. The unambiguous characterization of each constitutional isomer was made possible by careful examination of the symmetry environment experienced by each proton on their 1H-NMR spectra.