Vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds. Thermodynamic and experimental studies

Marek Gliński , Urszula Ulkowska

Abstract

This paper presents the first systematic thermodynamic study of the vapour phase transfer hydrogenation of α,β-unsaturated carbonyl compounds at temperatures: 423.15–723.15 K. Calculations were made for four compounds, namely: acrolein, α-methylacrolein, β-methylacrolein and methyl vinyl ketone. The Gibbs free energies and equilibrium mole fractions (EMFs) were calculated for transfer hydrogenation with ethanol and 2-propanol as hydrogen donors. It was noted that for transfer hydrogenation and hydrogenation with hydrogen the formation of the unsaturated alcohol (UOL) is the least thermodynamically favoured reaction and that saturated alcohol (SOL) and saturated aldehyde or ketone (SAL or SON) are the main products. A set of eight carbonyl compounds have been transfer hydrogenated with ethanol and 2-propanol in the presence of MgO as the catalyst. The main conclusions are that: (a) the reduction of a carbonyl group into a carbinol group occurs with a very high selectivity, (b) for almost all carbonyl compounds, except acrolein, the reactivity of 2-propanol highly exceeded that shown by ethanol and (c) the high chemoselectivity of transfer hydrogenation of acrolein with alcohols resulted from the kinetic control caused by the presence of magnesium oxide.
Author Marek Gliński KTCh
Marek Gliński,,
- Chair of Chemical Technology
, Urszula Ulkowska KTCh
Urszula Ulkowska,,
- Chair of Chemical Technology
Journal seriesApplied Catalysis A-General, ISSN 0926-860X
Issue year2016
Vol511
Pages131-140
Publication size in sheets0.5
Keywords in EnglishThermodynamic analysis; α,β-unsaturated carbonyl compounds; Hydrogenation; Transfer hydrogenation; Chemoselectivity
DOIDOI:10.1016/j.apcata.2015.11.046
URL http://www.sciencedirect.com/science/article/pii/S0926860X1530274X
Languageen angielski
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Score (nominal)40
ScoreMinisterial score = 40.0, 28-11-2017, ArticleFromJournal
Ministerial score (2013-2016) = 40.0, 28-11-2017, ArticleFromJournal
Publication indicators WoS Impact Factor: 2016 = 4.339 (2) - 2016=4.354 (5)
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