One-pot Synthesis Of Spirooxindole Derivatives In Water And Alkaline Proteinase-Catalyzed Henry Reaction

Following the main principle of green and "atom-economy", we described the research of the Henry reaction catalyzed by Alkaline Proteinase and multicompont and one-pot synthesis of spirooxindole derivatives in water catalyzed by IRA-900(Cl-) and catalyst-free in this thesis.Part 1:One-pot Synthesis of Spirooxindole Derivatives in WaterThe spirooxindole derivatives are an important class of heterocyclic spirooxindoles which often occur in nature products. Their synthesis has gained much attention recent years due to their biological and pharmacological activities. First, we tested the reaction of isatin, malononitrile and 1,3-Cyclohexanedione (mole ratio of 1:1:1, and 1.0 mmol) as a model reaction in water. The effects of different catalysts, the amount of water and temperature were investigated. The results showed that 10 ml water as solvent, IRA-900(Cl-) as catalyst and 25℃were optimized reaction conditions. Finally,19 spirooxindole derivatives were obtained in excellent yields (up to 99%) in water catalysed by IRA-900(Cl-). And then, we investigated catalyst-free reaction of isatin, malononitrile and 1,3-cyclohexanedione. The effects of the amount of water and temperature were discussed. The results showed that 20 ml water as solvent and 80℃were optimized reaction conditions. Finally,24 spirooxindole derivatives were obtained in excellent yields up to (93%) in water.Part 2:Alkaline Proteinase Catalyzed Henry ReactionHenry reaction was one of the most powerful C-C bond forming reactions in organic chemistry. And the enzyme-catalyzed reaction was efficient, environmental friendly and economical. In this thesis, the enzyme-catalyzed Henry reaction was investigated. The parameters, such as catalyst, solvents and temperature were optimized. The results showed that alkaline proteinase as catalyst, DMF as solvent and 25℃were optimal reaction conditions. Finally, the corresponding Henry products were obtained with yield up to 88% under the optimal conditions.