The Mechanism for Michael Addition of Methanethiol to 3-methyl-3-buten-2-one Catalyzed by Ionic Liquid [BMIM]OH
1. Department of Chemical Engineering and Safety, Binzhou University, Binzhou 256603, China;
2. College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
Abstract In order to better understand the role of the ionic liquids in the Michael addition reaction, the density function theory (DFT) B3PW91 method was employed to study the microscopic mechanism for the Michael addition of methanethiol to 3-methyl-3-buten-2-one in the ionic liquid ([BMIM]OH) with the 6-31G(d) basis settings. Geometric configuration of each stationary point was completely optimized on the potential energy surface. The results showed that in the absence of catalyst, the addition reaction energy barriers of the trans- and cis-configurations of 3-methyl-3-buten-2-one were 201.34 and 167.82 kJ/mol, respectively. When [BMIM]OH was used as the catalyst, the reaction energy barriers of the rate-determining step were reduced to 46.53 and 44.38 kJ/mol, respectively. The anion and cation of [BMIM]OH played important roles in the Michael addition, which increased the activity of Michael addition and decreased the reaction energy barrier significantly.
Bian He1,2,Zhang Huiming1. The Mechanism for Michael Addition of Methanethiol to 3-methyl-3-buten-2-one Catalyzed by Ionic Liquid [BMIM]OH[J]. 化学反应工程与工艺, 2018, 34(4): 379-384.
Bian He1,2,Zhang Huiming1. The Mechanism for Michael Addition of Methanethiol to 3-methyl-3-buten-2-one Catalyzed by Ionic Liquid [BMIM]OH[J]. 化学反应工程与工艺, 2018, 34(4): 379-384.
