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

• Autorzy: Qi-Shan Hu , Lai-Cai Li , Xin Wang
• Języki publikacji: EN

Abstrakty

EN

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·mol−1 less than the uncatalyzed reaction. The mechanism of the lithium ethoxide catalyzed reaction differed from the mechanism of the uncatalyzed reaction.

Słowa kluczowe

EN

Density functional theory; Lithium ethoxide; Transition state; Reaction mechanism

• Czasopismo: Open Chemistry
• Rocznik: 2008
• Tom: 6
• Numer: 2
• Strony: 304-309

Daty

wydano

2008-06-01

online

2008-04-17

Twórcy

autor

Qi-Shan Hu,

autor

Lai-Cai Li

• College of Chemistry and Material Science, Sichuan Normal University, Chengdu, 610066, People’s Republic of China

autor

Xin Wang

• College of Chemistry, Sichuan University, Chengdu, 610064, People’s Republic of China

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Identyfikatory

DOI

10.2478/s11532-008-0004-9