Design And Synthesis Of Fluorous Tailed Hyperbranched Catalysts Based On Behera's Amine And Their Application

High selectivity, high yield, atom economy, and the mild reaction conditions are new trends of the catalytic reaction, which make the development of multi-functional catalyst with high activity become very important. In the multi-functional catalytic system, multiple parts of a catalyst or multiple catalysts work together to promote a specific reaction.In recent years, many new and efficient catalysts have been developed and used to catalyze organic reactions, showing a good catalytic activity, which include the dendrimer catalysts and rare earth Lewis acid catalysts. However, dendrimer catalysts are not easily synthesized and rare earth Lewis acid catalysts are easily deliquescence. Based on the concept of surfactant-assisted rare earth catalytic system, combined with the merits of dendrimer catalyst and micelle catalyst of quaternary ammonium surfactant, a new quaternary ammonium salt containing perfluoroalkyl branch-like carboxylic acid and its rare-earth complex was designed and synthesized successflully. The stable and water repellent perfluoroalkyl chain stabilized the rare earth cation, prevent it from deliquescence; The complex of rare earth metals and carboxylic acid embedded in the periphery of the dendritic structure with high catalytic activity. As surfactant, perfluoroalkyl quaternary ammonium salt can form emulsion in the aqueous phase and make substrates disperse very well.Using Behera's amine as dendron, bromoacetyl bromide as a linker, perfluoroalkyl chain was introduced by nucleophilic substitution. Then, after quaternization and hydrolysis reaction, the multibranched carboxylic acid catalyst containing perfluoroalkyl quaternary ammonium salt was synthesized. By acylation with bromoacetyl bromide, Behera's amine was transferred to a useful intermediate, which has been used to react with various primary amines to afford dendritic catalyst containing 12 carboxyl groups or the surfactant Lewis base containing 6 carboxylate groups. This intermediate was also used to react with diethanolamine, then after amination reaction of the hydroxyl group, the product was hydrolyzed to afford the water soluble diethylenetriamine (DETA) ligand. In the process of preparation of the target molecule, it was found that bromoacetyl bromide was a highly activity and high efficient for the synthesis of dendritic molecules based on Behera's amine, which may become one of the efficient method to the synthesis of dendrimers.The CMC value was determined by testing surface tension of the surfactant catalyst with different carbon chains. Among all of them, the one containing single perfluorooctyl chain and two quaternary ammonium salt has the lowest CMC value of 10-4mol·L-1 with the surface tension of water reduced to 30 dyn.cm-1. At the same time, by comparing the results of water absorption properties of the catalyst in air, it was proved that the catalyst with perfluorooctyl chain has the best water resistant properties.The multibranched carboxylic acid catalyst with perfluoroalkyl quaternary ammonium salt was used to coordinate with rare earth Lewis acid and catalyzed the three components reaction of aldehyde, malononitrile and naphthol to afford 2-amino benzopyran derivatives with good results. Meanwhile, it could also be very effective in the catalysis of Hantzsch reaction. The catalyst could be recycled and reused for more than 3 times. Additionally, the water soluble DETA ligand could coordinate with PdCl2 and has been applied in Suzuki reactions in water, with the yield up to 90%. The catalyst was recovered and reused for three cycles. The surfactant Lewis base containing 6 sodium carboxylate groups was used to catalyze Henry reaction in water with the yield up to 96%, and the catalyst could easily be recycled and reused for more than 3 times. By the assistant of dendritic catalyst containing 12 carboxyl groups, benzyl alcohol derivatives could be oxidized by H2O2 with the yield up to 80%, avoiding the use of traditional heavy metal catalysts.In addition, this dissertation also includes the study of other types of green catalysis methodology. Ionic solid sulfonic acid was synthesized and used as heterogeneous catalyst to catalyze the addition reaction of indole and nitrobenzene to afford the products with moderate yields. By filtration and drying, the catalyst could be recovery and reused again. Finally, the cascade Knoevenagel condensation and Michael addition reaction of aldehydes and 1, 3-diketones in water and under catalyst free condition were explored, and the product can be purified just by filtration, washing and drying. The solvent-free amination of secondary benzylic alcohols with N-nucleophiles catalyzed by FeCl3 was also studied affording the products in good yields.