Theoretical study on the mechanism of reaction between 3‐hydroxy‐3‐methyl‐2‐butanone and malononitrile catalyzed by magnesium ethoxide |
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| Authors: | Lin‐Sen Heng Qi‐Shan Hu Lai‐Cai Li Xin Wang |
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| Institution: | 1. College of Bioinformation, Chongqing University of Posts and Telecommunications, Chongqing 400065, People's Republic of China;2. Department of Chemistry and Chemical Engineering, Sichuan University of Arts and Science, Dazhou 635000, People's Republic of China;3. College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610066, People's Republic of China;4. College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China |
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| Abstract: | The mechanism of reaction between 3‐hydroxy‐3‐methyl‐2‐butanone and malononitrile for the synthesis of 2‐dicyanomethylene‐4,5,5‐trimethyl‐2,5‐dihydrofuran‐3‐carbonitrile catalyzed by magnesium ethoxide was investigated by density functional theory (DFT). The geometries and the frequencies of reactants, intermediates, transition states, and products were calculated at the B3LYP/6–31G(d) level. The vibration analysis and the IRC analysis demonstrated the authenticity of transition states, and the reaction processes were confirmed by the changes of charge density at bond‐forming critical point. The results indicated that magnesium ethoxide is an effective catalyst in the synthesis of 2‐dicyanomethylene‐4,5,5‐trimethyl‐2,5‐dihydrofuran‐3‐carbonitrile from malononitrile and 3‐hydroxy‐3‐methyl‐2‐butanone. The activation energy of reaction with magnesium ethoxide decreased by 102.37 kJ mol?1 compared with that of the reaction without it. The mechanism of reaction with catalyst magnesium ethoxide differs from that of reaction without it. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 227–235, 2009 |
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