Synthesis&Immobilization Of Tin Porphyrins And Their Behaviour In The Catalytic Oxidation Of Alkenes

Oxidation of hydrocarbons with air or dioxygen is an extremely important reaction in chemical industry. A wide variety of catalysts have been used during the oxidation process, especially, the biomimic catalysts attract more attention due to the advantage of the high-efficiency, green, energy saving. Metalloporphyrins, as models and mimics of enzymes like catalase, paroxidases, cytochrome P-450, are widely and intensely investigated in the area of biomimic catalysis. Furthermore, metalloporphyrin is the active center of cytochrome P-450and applied to various fields, such as organic synthesis, catalysis, material, biomedicine. et al. So it’s very significant to study the oxidation of hydrocarbons catalyzed by metalloporphyrin derivatives.In this paper, The first chapter briefly introduced porphyrin and metalloporphyrin. Once more, we summarized selective oxidation of metalloporphyrin in homogeneous system and immobilized metalloporphyrin in heterogeneous system, as well as influence on the activity of metalloporphyrin by substituents. Finally, the paper expounded the current situation of catalytic oxidation of cyclohexene.The first chapter was the section of experiment. In this chapter, a series of metallo-deuteroporphyrin derivatives have been synthesized and their constructures were proved. Metal lo-deuteroporphyrin derivatives was synthesized from hemin, and modified the β-site of metallo-deuteroporphyrin dimethyl esters synthesizing a series of β-substituted deuteroporphyrin dimethyl esters. At last, we obtained the optimization of reaction conditions.Secondly, the second chapter and the third chapter mainly introduced catalytic oxidation of metalloporphyrin in homogeneous system. Taking Sn-DPDME as an example, the best results were obtained84%cyclohexene conversion and94%selectivity of the corresponding products in the presence of catalyst7.6×10-3mmol, temperature100℃, pressure0.8MPa, reaction time7h and10mL cyclohexene. Catalytic oxidation of cyclohexene by molecular oxygen was free radical reaction. Furthermore, under optimal reaction conditions we studied the catalytic properties of the β-site deuteroporphyrin dimethyl esters. Meantimes, we also studied the spectral properties and the stable properties of the β-site deuteroporphyrin dimethyl esters using UV-vis absorption spectroanalysis and high-energy collision-induced dissociation of tandem mass spectrometry.Finally, two kinds of supported catalysts, SiO2&NH2&Sn/Mn-DP and Fe3O4&SiO2&NH2 &Sn/Mn-DP were prepared by convalent binding of metallo-deuteroporphyrin ring to SiO2and Fe3O4, respectively. Their structures and properties were investigated by FTIR、TG-DTA、 TEM、SEM and XRD in the fourth chapter. We studied the optimum reaction conditions of catalytic oxidation of cyclohexene by oxygen and tne series of olefins reaction under the optimum reaction conditions.