Convenient synthesis of difurylmethanes and dithienylmethanes and their application to the syntheses of core-modified porphyrins

One flask synthesis of dithienylmethane and difurylmethane is reported. The reaction of aldehydes with excess furan or thiophene affords the meso-phenyldithienylmethane (DTM) and meso-phenyldifurylmethane (DFM), respectively. The reaction is catalyzed with trifluoroacetic acid or with BF3.O(Et)(2). An acyl group is selectively introduced in 1 and 9 position of difurylmethane and dithienylmethane by use of an acid chloride and tin (IV) chloride. The reduction of resulting 1,9-bisacyldifurylmethane or 1,9-bisacyldithienylmethane affords the corresponding 1,9-bis-diol. An acid catalyzed condensation of diol with meso-phenyldipyrromethane followed by oxidation with DDQ gives the porphyrins. The reaction resulted meso-5,10,15,20-tetraphenyl-21,22-dithiaporphyrin (SSNN) or 15-mesityl-5,10,20-triphenyl-21,22-dioxaporphyrin (OONN), respectively. The formation of small amount of meso-tetraphenylporphyrin (TPPH2) is also observed. The formation of TPP indicates that meso-phenyldipyrromethane is reversibly cleaved and form pyrrole and pyrrylbenzylcarbocation during the condensation. The proton nmr and electronic spectrum of the SSNN and OONN porphyrins are somewhat different from the previously synthesized meso-5,10, 15,20-tetraphenyl-21,23-dithiaporphyrin (SNSN) or meso5,10, 15,20-tetraphenyl-21,23-dioxaporphyrin (ONON).