Study On The Oxidation Of Benzothiazole Sulfides Catalyzed By Iron Porphyrin And Synthesis Of New Pocket Porphyrin

Metalloporphyrins as models of cytochrome P450attracted great attention in the fields of organic synthesis and biomimetic catalyst due to their remarkable catalytic properties. In this thesis, three kinds of benzothizolyl sulfides [n-butyl benzothiazolyl sulfide (BBT), allyl benzothiaolyl sulfide (ABT) and1,3-pentadiene benzothiazolyl sulfides (PBT)] were oxidized to the corresponding sulfoxides and sulfones catalyzed by tetra (o-chlorophenyl) iron (III) porphyrin under mild condition.The catalyst, tetra(o-chlorophenyl) iron (III) porphyrin, was prepared by using o-chlorobenzaldehyde and pyrrole with the improved Adler method. Three kinds of benzothiaolyl sulfides, BBT, ABT and PBT, were synthetized by ultrasonic irradiation, in68～92%yield, at room temperature.Then, we investigated the oxidation of the three kinds of benzothiaolyl sulfides BBT ABT and PBT, catalyzed by tetra (o-chlorophenyl) iron (III) porphyrin. The influence of oxidant, catalyst and temperature in the catalytic oxidation reaction was also discussed.Because most of the synthetic metal porphyrins, as models of enzymes, were usually lack of the enzyme’s protein part features and metal porphyrins’ molecules were prone to dimer themselves, many scientists had modified the metal porphyrins’ compounds by chemical methods. They usually introduced large hydrophobic barrier groups to the one side of porphyrins’ plane to simulate the natural enzyme protein environment and prevent metal porphyrins complexing with molecular oxygen to form dimer. In this thesis, we designed and synthesized a new kind of pocket iron porphyrin. Introducing3,3’,3"-(benzene-1,3,5-triyl) tripropanyl acyl groups at one side of the porphyrin plane simulate the iron porphyrin in natural enzyme protein environment. Catalytic propertie of the new pocket iron porphyrin was also measured.First, we determined the synthetic route of the intermediate of the new pocket porphyrin,3,3’,3"-(benzene-1,3,5-triyl) tripropanoic acid. Starting with trimesic acid, via esterification, reduction, bromine, diethyl malonate instead, Kraocho reaction and hydrolysis, intotal six steps to get the product, the overall yield was39.1%. The3,3’,3"-(benzene-1,3,5-triyl) tripropanoic acid was characterized by1H NMR and MS spectra etc.Then, we synthetized another intermediate of the new pocket porphyrin,5,10,15-tri-(o-aminophenyl)-20-phenyl porphyrin (TNH2PP), with o-aminobenzaldehyde benzaldehyde and pyrrole by the improved Adler method. The TNH2PP was characterized by1H NMR, MS spectra etc.Finally, we synthetized the new pocket porphyrin with the3,3’,3"-(benzene-1,3,5-triyl) tripropanoic acid and TNH2PP. The new pocket porphyrin was characterized by1H NMR, MS and UV spectra etc.We also explored the new pocket porphyrin’s catalytic property in the oxidation of methyl phenyl sulfide at room temperature.