Ab initio study of 1,3-dioxanes formation from formaldehyde dimer and alkenes

作者：Kupova O Yu^*; Vakulin I V; Talipov R F

来源：Computational and Theoretical Chemistry, 2013, 1013: 57-61.

DOI：10.1016/j.comptc.2013.02.024

• Ab initio calculation
• Transition state
• Prins reaction
• 1,3-Dioxanes
• Formaldehyde oligomers
• Alkenes

Some features of adding formaldehyde dimer to alkenes with formation of alkyl-substituted 1,3-dioxanes by the Prins reaction in the gas phase are studied at the MP2(fc)/6-31G(d,p) computational level. The structure of the transition states and key intermediates is revealed and thermochemical reaction parameters are determined. It is shown that 1,3-dioxanes are mostly formed from the it-complex obtained in the result of formaldehyde dimer interaction with alkenes without intermediate formation of a sigma-complex. Here the transformation of it-cation can be considered as a pseudo synchronous process. The synchrony degree and activation energy are considerably determined by the presence of alkyl substituents at the double bond.

• 出版日期2013-6-1