Theoretical study on the mechanism of reaction between 3-hydroxy-3-methyl-2-butanone and malononitrile catalyzed by lithium ethoxide

被引：2

作者：

Hu, Qi-Shan ^{[1
,2
]}

Li, Lai-Cai ^{[2
]}

Wang, Xin ^{[3
]}

机构：

[1] Sichuan Univ Arts & Sci, Dept Chem & Chem Engn, Dazhou 635000, Peoples R China

[2] Sichuan Normal Univ, Coll Chem & Mat Sci, Chengdu 610066, Peoples R China

[3] Sichuan Univ, Coll Chem, Chengdu 610064, Peoples R China

来源：

CENTRAL EUROPEAN JOURNAL OF CHEMISTRY | 2008年 / 6卷 / 02期

关键词：

density functional theory; lithium ethoxide; transition state; reaction mechanism;

D O I：

10.2478/s11532-008-0004-9

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The 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 lithium 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 verified the authenticity of transition states. The reaction processes were confirmed by the changes of charge density at the bond-forming critical point. The results indicated that lithium ethoxide is an effective catalyst in the synthesis of 2-dicyanomethylene-4, 5, 5-trimethyl-2, 5-dihydrofuran-3-carbonitrile from malononi-trile and 3-hydroxy-3-methyl-2-butanone. The activation energy of the reaction with lithium ethoxide was 115.86 kJ center dot mol(-1) less than the uncatalyzed reaction. The mechanism of the lithium ethoxide catalyzed reaction differed from the mechanism of the uncatalyzed reaction.

引用

页码：304 / 309

页数：6

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