Slelective Catalysis Of Metalloporphyrins For Aerobic Oxidation Of Double Bond And Allylic C-H Of Olefines

We used α -pinene as a substrate in order to investigate the catalytic selectivity of simple metalloporphyrins to double bond and allylic C-H of alkenes using air as oxidant in the absence of cocatalyst and solvents under mild conditions. Experimental results indicate that the reaction temperature, ions, and peripheral substituents play an important role on the α -pinene conversion and the selectivity to double bond and allylic C-H of α -pinene. And a potential mechanism is also proposed in this research.The contents of this thesis are presented as follows:1.The research and application of the alkenes were presented in the introduction, involving the development of metalloporphyrins in catalyzing alkenes oxidation. Furthermore, the theory of the substituent effects and linear free-energy relationship was also presented in detail.2.The different kinds of porphyrins and metalloporphyrins bearing different substituents which were synthesized and characterized were listed in the second chapter. The effect of the central metal iron and substituents at phenyl-ring on half-wave potential was also investigated.3.In the third chapter we introduced the studies of the catalytic oxidation of olefins. The design of the reaction equipment and the analysis methods to the products were showed at first. The selective catalysis of TPPMnCl for the oxidation of α -pinene with air was studied in the absence of cocatalyst and solvents for the first time, and 18.68% of conversion was gained. The effects of various parameters on double bond and allylic C-H of α -pinene, such as reaction conditions, nuclei, subsituents attached to phenyl-ring, were explored by means of serious experiments. And we introduced the effect of the central metal iron on the results of the α -pinene oxidations with air catalyzed respectively by monoironporphyrins. The results indicate that catalytic activity of MnTPPCl is higher than that of other metalloporphyrins.4.Selective catalysis of simply metalloporphyrins for α -pinene oxidation with air catalyzed by monoiron-porphyrins and monomanganese-porphyrins which all attached to substituents in this section. Hammett equations of the two series catalysts showed the comparison of the catalytic activity.5.In the fifth chapter, the electrochemical property of metalloporphyrins was introduced. And we investigated internal relation between electrochemical property of metalloporphyrins and its selective catalysis.6.In the end of this thesis we discussed the potential mechanism of the oxidation of olefins catalyzed by metalloporphyrins according to the results of some comparative experiments and literature reports. At the same time, a potential path way of α -pinene oxidation was also investigated. It illustrate the oxidation reaction of olefins is a radical mechanism, The main channels of the reaction between olefins and the active intermediate are addition to the double and H-atom abstraction from allylic carbon...