Synthesis And Structural Characterization Of Several Fragments Of The Tolyporphin Model

Tolyporphin is a kind of bacteriochlorins, which belong to natural cyclictetrapyrrole compounds. It plays an important role on chemical treatment and phototherapyof cancer so the research on its synthesis and application is presently an important studycontent and hotspots of the chemistry of natural products. In this dissertation, the methodsto synthesize tolyporphin model and its segments were summarized through the analysisand comparison to various synthesis methods of chlorins and pyrrole derivatives.The total synthesis way of the tolyporphin model was designed according to the"3+1" synthesis method. The synthesis of several pyrrole derivatives and adipyrrylmethene were studied, such as the ring-B,C,D building block of the tolyporphinmodel——3-methyl-1H-pyrrol-2(5H)-one, ethyl 3-bromo-5-formyl-4-methyl-1H-pyrrole-2-carboxylate and 5-bromo-4-methyl-1H-pyrrole-2-carbaldehyde, and B-C-semichlorinof the tolyporphin model——(Z)-ethyl 3-bromo-4-methyl-5-((4-methyl-5-oxo-1H-pyrrol-2(5H)-ylidene)methyl)-1H-pyrrole-2-carboxylate.The structures of the synthetic productswere characterized by elemental analysis, infrared (IR), ~1H nuclear magnetic resonance(NMR), gas chromatography (GO)and mass spectra (MS).The results came to the following conclusions: the tolyporphin model reflected thestructural characteristic of natural tolyporphin compounds; the structures and performanceindexes of the products conformed to the design requirement, the synthesis ways of thetarget compounds were brief and had good selectivity; the ring-C,D building block of thetolyporphin model were all synthesized sucessfully by two methods respectively; thesynthesis design of each compound was novel, practical and effective.