The Synthesis Of Unsymmetrical Tailed Porphrin Based Models

Porphyrins as synthetic biomimetic macromolecules, are widely used in catalyzing organic synthesis, molecular recognition, materials science and medicine etc. But the new porphrins reported are mostly tetraphenylporphyrins that based on5,10,15,20-tetraphenyl porphyrin(TPPH2). In this article, we synthesized a new porphrin with four benzene rings, but it has a double bond directly attached to the porphrin ring, which is different from TPPH2.By reducing the5,10,15,20-tetra(4-nitrophenyl) porphyrin with Stannous chloride dehydrate, three amino porphyrins were obtained that can be used as nonlinear optical materials. Amino group is an active base to develope for other functions. Therefore three unsymmetrical compounds with active bases can be serviced as the basic models for nonlinear properties and optical catalysts. In this article,5,10,15,20-tetra(o-nitrophenyl) porphyrin was reduced by stannous chloride dehydrate. And three amino porphyrins which have not previously been reported were obtained.5-styryl-10,15,20-triphenyl porphyrin(SPPH2) was synthesized using5-styryl dipyrromethane, benzaldehyde and pyrrole as starting materials and BF3-(C2H5)2O as catalysts. The new porphyrin was affirmed by MS,1H-NMR spectrum, UV-Vis spectrum and IR. We studied the stability of SPPH2and TPPH2(oxidized by30%hydrogen peroxide) at room temperature by UV-Vis Spectrophotometer.T(o-NO2)PPH2was reduced by stannous chloride dehydrate(SnCl2·2H2O). And then three different amino porphyrins were obtained. They were5-(o-aminophenyl)-10,15,20-tri(o-nitrophenyl) porphyrin(TAN3PPH2);5,10-di(o-aminophenyl)-15,20-di(o-nitrophenyl) porphyrin(TA3NPPH2) and5,10,15-tri(o-aminophenyl)-di(o-nitrophenyl) porphyrin (TA2N2PPH2). These three new synthetic amino porphyrins were characterized by elemental analysis, UV-visible spectrum and IR.The N-tert butylation of amino porphyrins was tried using the tert-butyl chloride as the alkylating reagent. But the target compounds were not obtained as expected.