76 Selective Reduction of Unsaturated Aldehydes and Ketones by a Vapor-Phase Hydrogen Transfer Reaction

Ballard, Seaver A.; Finch, Harry; Winkler, D. E.

doi:10.1016/s0360-0564(08)60228-x

Cited by 8 publications

(7 citation statements)

References 6 publications

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“…A description of low and high reactivities of alcohols has been given and the obtained values have been compared with those resulted from the thermodynamic calculations. Very high reactivity of ethanol as the hydrogen donor to acrolein observed for MgO [20,22], significantly exceeding that of propan-2-ol [21], has been confirmed by us. Moreover, we have also found that butan-1-ol is a very reactive hydrogen donor and the observed reactivities of ethanol and butan-1-ol are higher than those predicted by the thermodynamic calculations based on the following equation: acrolein ?…”

Section: Introductionsupporting

confidence: 60%

“…In the case of the above-mentioned exceptions, the experimentally determined yields of allyl alcohol greatly exceeded the thermodynamic yields for both donor-acceptor molar ratios (Table 7). The results obtained in the past for ethanol as hydrogen donor [20,22] also exceeded those predicted by thermodynamic calculation based on Eq. 3.…”

Section: Thermodynamic Description Of the Processmentioning

confidence: 66%

“…This maximum reached the value of 63-64% (D/A = 6) at chemoselectivities 88 and 81% for D/A = 6 and 9 (mol/mol) a UOL allyl alcohol, SAL propionaldehyde and SOL propan-1-ol ethanol and butan-1-ol, respectively. Only a slightly lower yield of allyl alcohol (55%) has been reported in the first publication on CTH of acrolein [20]. A much higher yield of allyl alcohol (73%) has been attained, however the catalyst was MgO-B 2 O 3 with propan-2-ol as the hydrogen donor [15].…”

Section: Catalytic Activity Measurementsmentioning

confidence: 92%

“…The first study on CTH of acrolein and other a,b-unsaturated carbonyl compounds was performed more than 50 years ago [20]. Oxides of magnesium, calcium, aluminum, zinc and cadmium, and a mixture of MgO-ZnO have been used as catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…Very little is known about the reasons of their reactivities besides the fact that they are weakly influenced by the structure of substituents surrounding the carbinol carbon atom. A higher reactivity of ethanol towards acrolein than propan-2-ol has been noted [20]. Moreover, in the CTH of a,b-unsaturated aldehydes other than acrolein, a much higher reactivity of propan-2-ol compared to that of ethanol has been observed [15,21].…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst

Gliński

Ulkowska

2010

Catal Lett

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This paper presents the first full thermodynamic description of the hydrogen transfer between acrolein, the simplest a,b-unsaturated aldehyde, and a set of aliphatic alcohols, both primary and secondary. The vapour phase transfer hydrogenation of acrolein into allyl alcohol with various primary and secondary aliphatic alcohols used as hydrogen donors in the presence of MgO as the catalyst has been studied. Despite differentiated reactivity exhibited by these alcohols, a high chemoselectivity ([80%) to allyl alcohol has been observed for all of them. On the basis of thermodynamic calculations it has been found that secondary alcohols as hydrogen donors are more reactive than primary ones. However, ethanol or butan-1-ol have shown the highest reactivity. In their presence yields of allyl alcohol higher than 60% have been noted, which greatly exceed those predicted by thermodynamic calculations based on the following equation: acrolein ? ethanol (butan-1-ol) ? allyl alcohol ? acetaldehyde (butyraldehyde). Although similar yields have been reported in literature, no subsequent nor side reactions have been discussed even though the attained yield cannot be accounted for by this reaction alone. As a possible explanation of the discrepancy the occurrence of a disregarded reaction, for which DG \ 0, has been considered. It has been shown that aldol condensation fulfills these thermodynamic requirements, however, the products of this reaction are noted only at the beginning of the process and the decrease of their amount does not influence the yield of allyl alcohol.

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Section: Introductionsupporting

confidence: 60%

Section: Thermodynamic Description Of the Processmentioning

confidence: 66%

Section: Catalytic Activity Measurementsmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst

Gliński

Ulkowska

2010

Catal Lett

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Enhancement of Tinctorial Strength of Non‐ammonia Caramels

1989

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Catalytic transfer hydrogenation of 2-butanone over oxide catalysts

Szőllősi

Bartók

1999

React Kinet Catal Lett

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Catalytic transfer hydrogenation of 2-butanone with 2-propanol was studied in gas phase over a series of oxides of different acid-base properties. Although the basic oxides (MgO, La203) gave high initial conversions, these oxides underwent deactivation during the reaction. This deactivation could be partially prevented by a previous treatment with chloroform of the oxide. The amphoteric oxides (TiO2, ZrO2, Al203) were also active in this reaction. Increasing the acidic character of the catalyst (Nb2Os, WO3) led to a pronounced dehydration of 2-propanol. The results obtained over a series of rare earth oxides (La203, Sm203, Gd203, Dy203, Er203) revealed that beside the role of basic and acid sites a correlation seems to exist between the number of unpaired electrons of the metal ion and the catalytic activity, indicating the role of one electron donor sites.

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76 Selective Reduction of Unsaturated Aldehydes and Ketones by a Vapor-Phase Hydrogen Transfer Reaction

Cited by 8 publications

References 6 publications

Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst

Reactivity of Alcohols in Chemoselective Transfer Hydrogenation of Acrolein over Magnesium Oxide as the Catalyst

Enhancement of Tinctorial Strength of Non‐ammonia Caramels

Catalytic transfer hydrogenation of 2-butanone over oxide catalysts

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