A new synthesis of pyrroles and porphyrins fused with aromatic rings

Abstract

Pyrroles fused with aromatic rings (isoindole derivatives) have been readily prepared by the reaction of aromatic nitro compounds with ethyl isocyanoacetate in the presence of DBU. The ease of this reaction depends on the aromaticity of the starting nitro aromatics. Polycyclic aromatic nitro compounds such as 1-nitroacenaphthylene or 9-nitrophenanthrene are more reactive than simple nitro aromatics such as nitrobenzene or nitronaphthalenes and give the corresponding pyrroles in good yields. Pyrroles prepared by this method have been converted into porphyrins fused with various aromatic rings by the reduction with LiAlH₄ followed by treatment with an acid catalyst and oxidation with chloranil or oxygen. Tetra-1,2-naphthoporphyrin has been prepared by the reaction of 2-nitro-3,4-dihydronaphthalene or 1-nitronaphthalene with ethyl isocyanoacetate followed by reduction, tetramerization and oxidation. Thus, highly conjugated porphyrins are readily prepared starting from aromatic nitro compounds, and their electronic and optical properties can be controlled by choice of the starting aromatic nitro compound.