Theoretical study of reaction mechanisms for the ketonization of vinyl alcohol in gas phase and aqueous solution

Oscar N. Ventura, Agustí Lledós, Rosanna Bonaccorsi, Juan Bertrán, Jacopo Tomasi

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58 Citations (Scopus)

Abstract

Theoretical ab initio calculations are done on different mechanisms for the conversion of vinyl alcohol to acetaldehyde, both in gas phase and in solution. Several basis sets are used in order to assess the accuracy of the results in gas phase and a continuum model of the solvent is employed to mimic reactions in water solution. The results indicate a catalytic action of water in hydrated clusters in gas phase, whereas in solution, and within the error limits of our calculations, both neutral water-chain and ionic mechanisms appear to be equally probable. Finally, the action of acids or bases is tested through the analysis of the reaction of vinyl alcohol with H3O+ and HO-. The results of the calculations are shown to be in qualitative agreement with the experimental facts when 6-31++G basis set is used but not when either STO-3G or 4-31G basis sets are employed. © 1987 Springer-Verlag.
Original languageEnglish
Pages (from-to)175-195
JournalTheoretica Chimica Acta
Volume72
Issue number3
DOIs
Publication statusPublished - 1 Jan 1987

Keywords

  • Ab initio methods
  • Keto-enolic tautomerism
  • Solvation energy
  • Vinyl alcohol

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