The Synthesis Exploration Of β-modifiedporphyrin Derivatives

This thesis studied the synthesis and exploration of β-modified porphyrin derivatives. Synthesis of α, β-unsaturated carbonyl porphyrins via Aldol condensation with solvent-free and optimization of synthesis method were studied. The ultraviolet-visible absorption spectra changes of this kind of unsaturated ketones porphyrin were checked. Exploration of the synthesis of porphyrin dimer carbocation by Aldol condensation, Wittig reaction and other methods, were carried out, and the synthesis of this compound needs further research. Although we did not obtain the target product product, other kinds of porphyrin derivatives were synthesized by chance. All structures of the synthesized compounds were characterized by 1H NMR, MS, IR and UV-vis.Part 1: The α, β-unsaturated carbonyl porphyrins was obtained by metallization, formylation and Aldol condensation using meso-tetraphenylporphyrin as starting materials. Part 2: The exploration of synthesis porphyrin dimer carbocationOne step synthesis and two step synthesis of porphyrin dimer carbocation precursor compounds were explorated by Aldol condensation, but target product were not acchieved.Using TPP-CHO as the raw material, the porphyrin phosphonium salt were gotten after reduction, chlorination and reacted with PPh3. Then the corresponding phosphonium salt reacted with acetylacetone by Wittig reaction, and only two kinds of corresponding porphyrin derivatives were generated.According to the literature methods, 2-formyl-meso-tetra(n-propyl) porphyrin reacted with acetone in the presence of piperidine and piperidine perchlorate, trying to get porphyrin dimmers through twice Aldol reaction. Eventually only α, β-unsaturated carbonyl porphyrin was resulted from only one molecule porphyrin by once Aldol reaction.