Theoretical study on the mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile catalyzed by magnesium ethoxide
✍ Scribed by Lin-Sen Heng; Qi-Shan Hu; Lai-Cai Li; Xin Wang
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 373 KB
- Volume
- 41
- Category
- Article
- ISSN
- 0538-8066
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✦ Synopsis
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