L. Heng, Q. Hu, Laicai Li
Apr 1, 2009
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0
Influential Citations
2
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Journal
International Journal of Chemical Kinetics
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