Synthesis Of Metallo-deuteroporphyrin Derivatives And Study On The Catalytic Oxidation Of Styrene

Metalloporphyrins exists widely in the nature. Some of them can mimic the cytochrome P-450well, so they can effectively activate oxygen make it transfer to substrates. Therefore, much special attention from both domestic and foreign scholars has been focused on these metalloporphyrins, which have been used as catalysts in different kinds of catalytic oxidation reactions. At present, the porphyrin catalysts involved in catalytic oxidation reactions are mostly based on tetraphenyl-porphyrin derivatives achieved by artificial synthesis, which owns low catalytic activity and poor selectivity. Compared with tetraphenyl-porphyrin, natural hemin can be achieved from a variety of sources and its structure is closer to the prosthetic group of natural cytochrome P-450enzymes, which makes it own higher catalytic activity and selectivity.In the paper, metallo-deuteroporphyrin derivatives were prepared from the extractive protohemin of natural hemin by several steps including eliminating vinyl, demetalation, acylation, esterification, reduction, diazotization and complexation. The catalytic activity of them have been studied in the oxidation of styrene with both tert-butyl hydroperoxide and oxygen as the oxidant, respectively. We have also investigated the catalytic activity of the catalysts. The contents of this thesis are presented as follows:(1) In the experiment, a series of deuteroporphyrin derivatives have been synthesized by means of the modification on the propionate side chains at13,17-sites of deuteroporphyrin and the mesoposition of deteroporphyrin dimethyl ester; and then, these deuteroporphyrin derivatives complexed with metal ion, especially for the manganese ion, synthesizing relevant metalloporphyrins. In addition, optimization of reaction conditions was sum up; in the end, the structures of those substances above were proved by MS, IR,1H NMR, UV-Vis and elementary analysis, respectively.(2) In the presence of tert-butyl hydroperoxide, metallo-deteroporphyrin dimethyl esters were used as catalysts in the oxidation of styrene under the atmosphere of normal pressure. We have optimized reaction conditions. On this basis, Mn-DPDME has the highest catalytic activity and the conversion of styrene and the selectivity of benzaldehyde are98.3%and92.7%, respectively. Besides, the mechanism of the reaction was also discussed.(3) A series of metalloporphyrin derivatives were used as catalysts in the oxidation of styrene, in which oxygen was regarded as the oxidant. Likewise, reaction conditions have been optimized. Under the condition, Mn-DPEDN showed the best catalytic potential and the conversion of styrene and the selectivity of benzaldehyde reached93.4%and90.7%, respectively. On the other hand, We have investigated the influence of substituents on catalytic activity and described the formation of intramolecular axial ligand of manganese niacin-porphyrins. Moreover, the relationship between the catalytic activity of niacin-porphyrins and their axial ligands has also been studied.