Synthesis and Separation of Structural Isomers of 2(3),9(10),16(17),23(24)-Tetrasubstituted Phthalocyanines

The 2(3),9(10),16(17),23(24)‐tetrasubstituted metalphthalocyanines 1–7 (M=In, Ni, Zn) were synthesized, as mixtures of four different structural isomers, from the corresponding 4‐alkoxy‐1,2‐dicyanobenzenes and the appropriate metal salts. Separation of the four structural isomers was successfully achieved on a C30 alkyl phase by high‐performance liquid chromatography (HPLC). The determination of the point groups of the structural isomers was carried out for 1 and 3, the composition of the structural isomers of 4–7 was accomplished by comparing their retention times and UV/Vis spectra with the data of 1 and 3. For the phthalocyanines 8–10 and the naphthalocyanines 11 and 12 only the C4h and D2h isomers could be separated. Die Synthese von neuen 2,3‐tetraalkenyloxy substituierten Phthalocyaninen mit verschieden langen Alkenylketten und unterschiedlichen Zentralmetallen, sowie die Separierung der vier Strukturisomere mittels HPLC (C30‐Phase) ist Thema dieser Arbeit. Charakterisierung der einzelnen Isomere erfolgte durch 1H NMR‐ und UV/Vis‐Spektroskopie. Die Untersuchung des sterischen Einflusses der Substituenten sowie der Einfluß des Zentralmetalls auf den Trennprozess und die Isomerenzusammensetzung ist hierbei von besonderem Interesse. Synthesis of new 2,3‐tetraalkenyloxy‐substituted phthalocyanines (an example is depicted here) and their HPLC separation of the four structural isomers with a C30 phase are reported. The determination of the point groups of the separated isomers is done by 1H NMR and UV/Vis spectroscopy. The steric hindrance of the different alkenyloxy substitutent and the influence of the central metals for the separation process and their distribution are investigated.