<Emphasis Type="Italic">Ab initio</Emphasis> quantum-chemical study of the reaction mechanisms of acetylene in superbasic media. Noncatalytic vinylation of methanol |
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Authors: | E Yu Larionova N M Vitkovskaya V B Kobychev N V Shevchenko B A Trofimov |
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Institution: | 1.Irkutsk State University,Irkutsk;2.A. E. Favorskii Institute of Chemistry, Siberian Division,Russian Academy of Sciences,Irkutsk |
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Abstract: | The reaction profile of noncatalytic vinylation of methanol with acetylene was studied by ab initio quantum-chemical calculations for the gas phase and by calculations using a combined model that took into account the solvent (DMSO) effect. The reaction occurs via the formation of a prereaction complex of the methoxide ion with acetylene; at this stage, the acetylene molecule is already activated with respect to the proton. The observed stereospecific trans-addition in methanol vinylation in the gas phase and solution is provided by the lower activation barrier corresponding to the E structure of the acetylene molecule in the transition state and barrier-free protonation of the carbanion intermediate. |
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