Synthesis Of Several Pharmaceutical Intermediates By Catalytic Oxidation Over Some Mesoporous Materials

Mesoporous materials have many potential applications due to their large specific surface area, large pore volume, uniform pore size, controllable morphology, and easily functionalized surface. So they are of great interest at present from viewpoint of both application and fundamental research. Meanwhile, biotemplating method has attracted considerable attention in order to fabricate materials with varied morphology because they are generally inexpensive, abundant, and environmentally benign. The templates can be easily removed by thermal decomposition, resulting materials that are replicas of their original shapes. Particularly, the well-ordered mesoporous materials incorporated with metal ions, have a good use in catalysis because of their unique properties. Therefore, it was suggested a good possibility to apply transition metal doped mesoporous materials as a catalyst for the syntheses of some important pharmaceutical intermediates. The conditions of catalytic reactions were optimized to achieve high conversion rates and selectivities.The major research results are drawn as follows:1. Cobalt doped mesoporous alumina prepared using natural rubber latex as template (Co/MAl2O3/RL) was used for selective catalytic oxidize tetralin and boromotoluene to tetralone, bromobenzoic acid respectively. The conversion rate of tetralin was80.3%, and the selectivity of tetralone was74.5%, while the conversion rate of m-bromotoluene was95.9%, the selectivity of m-bromobenzoic acid was95.6%. Cobalt doped mesoporous silica prepared using natural rubber latex as template (Co/SiO2RL) was used for selective catalytic oxidize boromotoluene to bromobenzoic acid, the conversion rate of m-bromotoluene was82.7%, the selectivity of m-bromobenzoic acid was80.5%. And cobalt doped mesoporous silica prepared using dioscorea opposita latex as template (Co/MAl2O3/DL) was used for selective catalytic oxidize boromotoluene to bromobenzoic acid, the conversion rate of p-bromotoluene was95.2%, the selectivity of p-bromobenzoic acid was85.8%.2. Cobalt-doped mesoporous titania synthesized by using skins of various plants as templates was used for selectively catalytic oxidize tetralin to tetralone. The effects of catalytic conditions on the performance of Co-Ti-BO were investigated. The conversion rate of tetralin was66.3%, and the selectivity of tetralone was65.1%. It was found that Co-Ti-BO showed a higher catalytic activity than CO/MTiO2prepared by using the dodecylamine as template.3. Transition metals doped MCM-41, mesoporous titania with anatase crystalline structural wall, TiO2-SiO2, Al2O3and SiO2, were also prepared. They were characterized by a combination of physicochemical techniques such as nitrogen adsorption/desorption measyrment, XRD, SEM, FT-IR and UV-Vis spectroscopy. The results showed that transition metals were well dispersed.4. Fe, Co, Ni, V, Ce, Cu, La, Zr, Cr doped MCM-41were used for selectively catalytic oxidize tetralin and boromotoluene to tetralone and bromobenzoic acid. The effects of catalytic conditions on Co/MCM-41and V/MCM-41catalytic oxidation were discussed. When Co/MCM-41was used as a catalyst, the conversion rate of tetralin was94.7%, and the selectivity of tetralone was70.3%. While the conversion rate of o-bromotoluene was96.2%, the selectivity of o-bromobenzoic acid was86.6%. When V/MCM-41was used as a catalyst, the conversion rate of tetralin was89.9%, and the selectivity of tetralone was72.5%.5. Co doped mesoporous titania modified with silica with Ti/Si molar ratio of0.4,0.5and0.6(Co-TiO2-SiO2) was used for selectively catalytic oxidize tetralin to tetralone. The effects of catalytic conditions on the performance of the catalyst were investigated. The conversion rate of tetralin was97.6%, and the selectivity of tetralone was75.5%. It was found that Co-TiO2-SiO2with Ti/Si molar ratio of0.6showed the highest activity.6. V, Mn, Fe, Co, Ni, Cu, Zn doped TiO2(M/MTiO2) and cobalt-M (M=Fe, V, Mo, La, Ni, Mn) co-doped TiO2(Co/M/MTiO2) were used for selectively catalytic oxidation of tetralin and boromotoluene to tetralone and bromobenzoic acid respectively. The effects of catalytic conditions-on the results were discussed. When V/MTiO2was used as a catalyst, the conversion rate of tetralin was92.5%, and the selectivity of tetralone was58.0%. When Co/Mn/MTiO2was used as a catalyst, the conversion rate of tetralin was58.0%, and the selectivity of tetralone was81.9%. When Co/Ni/MTiO2was used as a catalyst, the conversion rate of p-bromotoluene was97.3%, and the selectivity of p-bromobenzoic acid was93.1%. When Co/Fe/MTiO2was used as a catalyst, the conversion rate of o-bromotoluene was97.5%, and the selectivity of o-bromobenzoic acid was85.6%. And Co/Ni/MTiO2was the best catalyst for the oxidation of p-bromotoluene.