Abstract: Core-modified porphyrins, in which one or more internal nitrogen atoms are replaced with other heteroatoms or carbon, have shown some novel properties such as stabilizing unusual metal oxidation states, catalysis, and photodynamic therapy(PDT), and nonlinear optical properties. To systematically exploit the distinctive properties of core-modified porphyrins requires the ability to locate not only the heteroatom in the core of the porphyrin but also arrange substituents about the porphyrin perimeter. In this article, an effective process to synthesize dithiaporphyrin derivatives was achieved. The key intermediates with one or two pyrrole groups could be selectively synthesized by treating unsymmetrical thiophene with TFA or BF₃·Et₂O, respectively. The structures of these dithiaporphyrins were charcterized by ¹H NMR spectra, ESI-MS, HR-MS, IR, UV-Vis spectra and fluorescence spectra.

Key words: Dithiaporphyrin, TFA, BF3·Et2O, Catalysis