Selective Synthesis Of Sulfones Based On Metalloporphyrins Complex

Sulfones are useful synthetic intermediates in organic chemistry and bioactive compounds for pharmacy, biochemistry and petroleum industry. The chemical synthesis of sulfones has important theoretical and practical values. Sulfones are generally prepared via oxidation of the corresponding sulfide or sulfoxide. Metalloporphyrins can simulate cytochrome P-450 to achieve the catalytic oxidation of substrates under mild conditions. This thesis presents the study on the oxidation of dibenzothiophene catalyzed by metalloporphyrins with molecular oxygen as oxidant in the absence of co-reductant or sacrificial agent.First, we synthesized series of metalloporphyrins with different central ions and different substituents, such as TClTPPFeCl/TClTPPMnCl, MNTPPFeCl/MNTPPMnCl, TNTPPFeCl/ TNTPPMnCl and THTPPFeCl. The structures of the catalyst were affirmed by IR, UV-Vis spectrum and 1H-NMR spectrum. The solubility of the porphyrin complexes in decalin were examined at room temperature by the simple method based on UV-Vis Spectrophotometer. Moreover, the central ions and the effect of the substitute on the catalyt's thermostability were studied.Secondly, by using the metalloporphyrins synthesized as catalysts, molecular oxygen as oxidant, we studied the selectively oxidation of DBT, diphenyl sulfide and other sulfide to corresponding sulfones in the oil, then investigated the effect of the substitute on the catalytic activity. We preliminarily studied its dynamics and the mechanism of the oxygenation is then proposed.Finally, we investigated the stability of the porphyrin complex during the oxygenation. Under the optimal oxidative condition, the factors of reaction temperature, reaction time, reaction pressure and the effect of ligand are investigated in detail. The mechanism of the porphyrin catalyst's self oxygenation is then discussed.