Study On The Reactions With α,β-Unsaturated Ketone Catalyzed By Amine Functionafized MCM-41and Heteropoly Acids

Michael addition in organic synthesis is one of the most efficient ways to build acarbon-carbon or carbon–mix bonds, their derivatives play an important role inorganic synthesis and drug synthesis, therefore, research in this area has causedwidespread attention. Usual catalysts of Michael addition reaction are proline and itsderivatives, imidazoline derivatives and cinchona alkaloids and so on, however,mesoporous materials as catalyst have been used less in this type of reaction. In thispaper, based on the work of the Task Force we investigated amime functionalizedMCM-41catalyzed Michael addition reaction of α,β-unsaturated ketones withmalononitrile, α,β-unsaturated ketones with hydrazine.Hydrazone compounds with C=N double bond is not only a precursor of manyreactions, but also has good pharmacological activity, such as therapeutic antibacterial,antispasmodic, anti-inflammatory, anti-platelet, anti-malarial, anti-cancer activity andso on. In addition, hydrazone compounds as Schiff bases has important applications inorganic synthesis, therefore, preliminary work on the basis of a combination of ourgroup, heteropoly acid catalyzed condensation reaction of α,β-unsaturated ketone withhydrazide, the reaction series of optimization, and a dozen substrates were expandedto obtain a good yield, up to99%.This thesis is divided into the following two parts:The first part of the literature review describes the features of heterogeneouscatalysts amine functionalized MCM-41(3-aminopropyltriethoxysilane immobilizedonto the mesoporous MCM-41) applied research in organic synthesis reactions;Michael addition reaction research progress of α, β-unsaturated ketone withmalononitrile, Aza-Michael addition reaction and condensation reaction researchprogress of α,β-unsaturated ketone with hydrazine.1.3-aminopropyltriethoxysilane was immobilized on mesoporous MCM-41and was characterized by means of IR, TEM, SEM and XRD methods.2. Amine functionalized MCM-41catalyzed Michael addition reaction of α, β-unsaturated ketones with malononitrile. When the reaction conditions are10wt%theamount of catalyst,0.5mL CH3OH at room temperature for24h, template reactioncan get the best results. Then under the optimal reaction conditions chalconesubstrates with different substituents were investigated, the number of cyanoderivatives were achieved, highest yield up to99%. Finally, the catalytic life of thecatalyst was inspected, the catalyst recycled times to maintain a good catalytic activity(78%yield).3. Amime functionalized MCM-41catalyzed Aza-Michael addition reaction of α,β-unsaturated ketones and hydrazide. In the preferred reaction conditions (solventCH3OH (0.5mL), substrate ratio1:1.2, the amount of catalyst15wt%0.003g,reaction time24h), the substrates were expaned, the substrate of the chalcones,substituted whether an electron-withdrawing group or electron donating group, theaddition product can be obtained smoothly. Hydrazide substrate also can be a goodyield; cinnamon when one substrate is selected, the condensation product wasachieved.4. On the basis of the third section of the experiment, we examined heteropolyacid catalyzed condensation reaction of α, β-unsaturated ketone with hydrazine. Inmethanol,20wt%phosphotungstic acid as the catalyst, benzylidene acetophenonewith benzoyl hydrazine (ratio1:1.5) obtained96%yield. In the universality inspectionof the substrate, chalcones, cinnamon chalcone and hydrazide can get a good yield.