Nano Mn₃O₄ Catalyzed Oxidation Reaction And Nano Bismuth Mediated Crotylation Reaction

With the development and combination of nanotechnology and green synthesismethodologies, nanocatalyts have attracted widely attention in both academic andindustrial areas.This thesis mainly study on nano Mn₃O₄-catalyzed green synthesis methods and theapplication for the oxidation reaction. Mealwhile, this thesis focuses on theshape-selective crotylation reaction mediated by nano bismuth in aqueous media.Firstly, we have synthesized Mn₃O₄nanoparticles and Mn₃O₄nanoparticles ondifferent templates, which have been employed in organic synthesis. There are threeparts included in this thesis for the study on Mn₃O₄nanoparticles. The first part isabout Mn₃O₄nanoparticles catalyzed the aerobic oxidation of various alcohols.Oxidation of alcohols to the corresponding carbonyl products is one of the mostfundamental reactions in organic chemistry. Moreover, Mn₃O₄nanoparticles exhibitedvery high selectivity in the aerobic oxidation of mixed alcohols. The catalyticselectivity perhaps originated from the selective chemisorption of alcohols on thesurface of the Mn₃O₄nanoparticles. The recyclability of Mn₃O₄nanoparticles catalystwas excellent. Its catalytic activity in the aerobic oxidation of benzyl alcohol didn'treduce even after 10 cycles of catalytic activity evaluation. The second part includesone-pot synthesis of 3, 4-disubstituted coumarins under catalysis of Mn₃O₄. We havesuccessfully developed a new catalytic system for one pot synthesis of 3,4-disubstituted coumarins by using Mn₃O₄nanoparticles as heterogeneous catalyst.The method is simple and Mn₃O₄nanoparticles display feature advantages, such aslow loading, high activity and good recyclability. In the third part we report a cheapand reusable heterogeneous catalyst SMONP-1(diatomite supported Mn₃O₄nanoparticles) catalyzed the oxyalkylation of vinylarenes and cyclic ethers. Invirtue of this SMONP-1, the corresponding products can be obtained with highregioselectivities and good yields. The reaction condition is mild and the catalystcan be reused for 4 times. Efforts to apply this heterogeneous catalyst to otherorganic reactions are in progress in our laboratory.As suggested by our previous study, the yield of the allylation reaction could beimproved by using metal nanoparticles. Furthermore, the shapes of nanoparticles could have an influence on the selectivity of the crotylation reaction. In order tofurther this idea, we have parparaed bismuth nanoparticles of different shapes,including nanoparticles, nanofilms, nanotubes and nanowires, which have been usedin the crotylation reaction of aldehydes in aqueous media. We could obtain highselectivity by changing bismuth nanoshapes. The reaction can be carried out smoothlyin water without organic solvents under mild conditions. The present work makescontribution to utilizing metal nanoparticle varied in shapes into organic synthesis.