Synthesis And Characterization Of Novel Chiral Camphor Porphyrin Ligand And Its Complexes

Porphyrin derivative is a special compound which contains macrocyclic aromatic conjugation system.Because of its unique structure and predominant physics,chemistry and optics characters,it has wide application foreground in various fields,such as biomimetic chemistry,material chemistry, medicinal chemistry,electrochemistry,photochemistry,analytical chemistry and organic chemistry.While,the chiral metalloporphyrin as an asymmetric catalyst not only has the excellent properties mentioned above but also has the capability of catalyzing asymmetric epoxidation of alkenes reaction,asymmetric cyclopropan reaction,asymmetric aziridinatic reaction,asymmetric hydroxylation reaction,asymmetric nitrogen-atom transfer reaction,asymmetric S-H insertion reaction and asymmetric oxidation of sulfide reaction in mild condition.So,synthesis of new kinds of chiral porphyrins as the catalysts to synthesize organic compounds with high selectively and efficiently in mild condition and explainning its catalysis mechanism is a hot topic.In this thesis,5,10,15,20-tetra-(4-nitrophenyl)porphyrin is synthesized by Adler method,and reduced by tin dichloride to prepare 5,10,15,20-tetra-(4-aminophenyl)porphyrin in HCl which is acylated by D-camphononic formyl chloride,two new chiral porphyrins were synthesized.One is 5,10,15-tri-(4-D-camphononicamidephenyl)-20-(4-aminophenyl)porphyrin,the other is 5,10,15,20-tetra-(4-D-camphononicamidephenyl)porphyrin.5,10,15,20-tetra-(4-D-camphononicamidephenyl) porphyrin as the ligand coordinated with seven salts including Co(â…¡),Ni(â…¡),Cu(â…¡),Mn(â…¡), Zn(â…¡),Ag(â… ),Ga(â…¢) ions respectively.Finally,Seven new chiral metalloporphyrins were prepared.Their molecular structures were characterized and studied by IR,NMR,UV-vis and fluorescence spectrums.And the relationships between the spectrums and the structures were also studied and explained by data arranging and analyzing.There are four chapters in this thesis:Chapter one:review on the synthesis methods of the porphyrin and the chiral porphyrin,briefly introducing the catalysis of the porphyrin,especially the asymmetric catalysis of the chiral porphyrin.Chapter two:prepareing two kinds of free porphyrins and seven metalloporphyrin complexes which are characterized by IR,NMR,UV-vis and fluorescence spectrums.Chapter three:studying and explaning on the special spectrums of the nine new porphryrins by data assigning and analyzing.Chapter four:summarizing the whole thesis.