| The oxidation of toluene in side-chain is a extremely important reaction in chemical industry, the major products, benzaldehyde, benzyl alcohol and benzoic acid are widely applied in food, spices, medicine, pesticides and other chemical industries. At present, the toluene oxidation steps of industrial production have many shortcomings, such as, a complex process, a large amount of catalyst, discharging massive pollutants. These methods don't conform to the development of green chemistry. In particular, the industrial products of benzaldehyde contain halide with the result that severely restricted the range of applications. Therefore, the studies on liquid phase oxidation to selectively produce benzaldehyde, benzyl alcohol using more green reaction conditions are of great significance.Here, we reported a new method of liquid phase oxidation of toluene to benzaldehyde and benzyl alcohol with dioxygen catalyzed by metalloporphyrins and NHPI in presence of simple aliphatic alcohols based on the results gained by formers in our group. we have founded firstly that the simple aliphatic alcohols such as methanol and ethanol have a huge promotion in the biomimetic oxidation system. It develops a new way on liquid phase selective catalytic oxidation of toluene. This thesis provides new materials in the field of theoretic and application aspects of biomimetic oxidation of hydrocarbons by metalloporphyrins.In this paper, we firstly summarized the recent advances on the main methods for toluene oxidation, axial coordination of metalloporphyrins with the alcohols and related catalytic mechanism about metalloporphyrins or NHPI system, and explained the significance of toluene oxidation, as well as the source of topics, significance and main contents.Secondly, nine different metal centers or different axial anions metalloporphyrins had been synthesized and characterized, their names Respectively are T(p-Cl)PPFeCl, T(p-Cl)PPCo, T(p-Cl)PPCu, T(p-Cl)PPMnF, T(p-Cl)PPMnCl, T(p-Cl)PPMnBr, T(p-Cl)PPMnI, T(p-Cl)PPMnOAc, T(p-Cl)PPMnSCN. As well as, we researched the similarities and differences among this metalloporphyrins by UV-Vis spectra in CH2Cl2 at room temperature.Thirdly, A GC internal quantitatively analyze method were built, and the quantitatively analyze method was optimized and tested. It has the advantages of high sensitivity, brilliant selectivity, good accuracy, simplicity and rapidity.Fourthly, the promotion from simple aliphatic alcohols on aerobic oxidation of toluene catalyzed by the metalloporphyrin and NHPI was studied. Both the structure and amount of aliphatic alcohols have a great influence on the reaction. The effects of reaction conditions, such as temperature, amount of catalyst, flow of oxygen, concentration of toluene, different metalloporphyrins and the oxidation products of methanol were investigated.Fifthly, the axial coordination of the nine metalloporphyrins with five Aliphatic alcohols (methanol, ethanol, propanol, isopropanol, tert-butanol) and two aromatic alcohols (benzyl alcohol,2-phenyl ethanol) was studied by UV-Vis spectrophotometry at room temperature in CH2Cl2. Here, we had investigated the axial coordination of T(p-Cl)PPMnF with CH3OH in details, and got get their coordination number and equilibrium constant. The effect of acetic acid on the axial coordination was also reported.Sixthly, the possible two pathways for simple aliphatic alcohols to promote the oxidation were analysed and demonstrated. the possible reaction intermediates were detected by UV-Vis spectra. On the basis of the well studied mechanism about metalloporphyrin and NHPI, we proposed a novel mechanism of catalytic cycle in the aerobic oxidation of toluene with dioxygen catalyzed by metalloporphyrin/NHPI in the promotion of simple aliphatic alcohols, is called the biological-chemical-cycle coupling mechanism.
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