The rhodium-promoted guerbet reaction

Burk, Patrick L.; Pruett, Roy L.; Campo, Kathryn S.

doi:10.1016/0304-5102(85)85012-4

Cited by 44 publications

(23 citation statements)

References 7 publications

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“…148,149 Contrary to the Rh-based catalysts studied by Burk et al, 92,147 Ir complexes remained active even without removal of water and with KOH instead of potassium alkoxides. However, 1,7-octadiene was used as a hydrogen acceptor, promoting dehydrogenation in order to obtain high yields of Guerbet alcohols, and the reaction took place at 120°C with the reagents diluted in p-xylene.…”

Section: Catalysis Science and Technology Minireviewmentioning

confidence: 69%

“…Although the presence of CaO as a water scavenger showed certain improvement of the catalytic performance, the best n-butanol conversion was obtained by increasing the reaction temperature up to 280°C (61% after reaction for 6 h). Burk et al 92,147 evidenced the synergistic interaction between the metal and the basic component when the selfcondensation of n-butanol to 2-ethyl-1-hexanol at low temperatures in the presence of Rh/C and sodium butoxide was performed. It was concluded that the initial dehydrogenation step requires the catalysis of both the transition metal and the base, whereas the α,β-unsaturated aldehyde derived from aldol condensation might be reduced to the Guerbet alcohol through two pathways; one is promoted only by the base and the other characterized by the successive assistance of both catalytic components.…”

Section: Catalysis Science and Technology Minireviewmentioning

confidence: 99%

“…This mechanism involving aldolization is supported by several arguments. Intermediate products of the pathway are often observed 92,[94][95][96][97][98] and can be reduced to the product alcohol under the same conditions. 70,96 The conditions applied in the Guerbet reaction are suitable for aldol condensation.…”

Section: Reaction Mechanisms and Thermodynamic Considerationsmentioning

confidence: 99%

“…As one reagent is converted into two products, a decrease in partial pressure of the alcohol will shift the equilibrium towards the aldehyde. The dehydrogenation reaction is often identified as the rate limiting step, in particular when lower temperatures 100 or higher hydrogen partial pressures 81,92 are applied, for instance with low boiling point alcohols in liquid phase reactions. Kinetically, the conversion of the feed alcohol into an aldehyde will be promoted by consumption of the aldehyde in the subsequent reaction steps.…”

Section: Reaction Mechanisms and Thermodynamic Considerationsmentioning

confidence: 99%

“…For instance, the Guerbet selfcondensation of n-butanol produces 2-ethylhexanol (2EH), industrially the most important compound in the group of "plasticizer alcohols". 5,[90][91][92] It is mostly applied in the synthesis of polymer additives, e.g. as a phthalate ester in PVC applications, giving the polymer improved flexibility and durability.…”

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confidence: 99%

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Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

Gabriëls

Hernández

Sels

et al. 2015

Catal. Sci. Technol.

243

233

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The Guerbet condensation reaction is an alcohol coupling reaction that has been known for more than a century. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of value chains of renewable chemical and biofuel production. Due to the specific branching pattern of the alcohol products, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. This review provides thermodynamic insights and unravels the various mechanistic steps involved. A comprehensive overview of the homogeneous, heterogeneous and combined homogeneous and heterogeneous catalytic systems described in published reports and patents is also given. Technological considerations, challenges and perspectives for the Guerbet chemistry are discussed.

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Section: Catalysis Science and Technology Minireviewmentioning

confidence: 69%

Section: Catalysis Science and Technology Minireviewmentioning

confidence: 99%

Section: Reaction Mechanisms and Thermodynamic Considerationsmentioning

confidence: 99%

Section: Reaction Mechanisms and Thermodynamic Considerationsmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

Gabriëls

Hernández

Sels

et al. 2015

Catal. Sci. Technol.

243

233

View full text Add to dashboard Cite

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Amyl Alcohols

Papa¹

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Amyl alcohol describes any saturated aliphatic alcohol containing five carbon atoms. This class consists of three pentanols, four substituted butanols, and a disubstituted propanol, ie, eight structural isomers C 5 H 12 O: four primary, three secondary, and one tertiary alcohol. In addition, 2‐pentanol, 2‐methyl‐1‐butanol, and 3‐methyl‐2‐butanol have chiral centers and hence two enantiomeric forms. The odd‐carbon structure and the extent of branching provide amyl alcohols with unique physical and solubility properties and often offer ideal properties for solvent, surfactant, extraction, gasoline additive, and fragrance applications. Today the most important industrial process for amyl alcohol production is low pressure rhodium‐catalyzed hydroformylation (oxo process) of butenes. Mixtures of isomeric amyl alcohols (1‐pentanol and 2‐methyl‐1‐butanol) are often preferred because they are less expensive to produce commercially and have a more desirable combination of properties. With the exception of neopentyl alcohol (mp 53°C), the amyl alcohols are clear, colorless liquids under atmospheric conditions, with characteristic, slightly pungent and penetrating odors. Commercial primary amyl alcohol is a mixture of 1‐pentanol and 2‐methyl‐1‐butanol. Like the lower alcohols, amyl alcohols are completely miscible with numerous organic solvents and are excellent solvents for nitrocellulose, resin lacquers, higher esters, and various natural and synthetic gums and resins. However, in contrast to the lower alcohols, they are only slightly soluble in water. Important amyl alcohol reactions include dehydration, esterification, oxidation, amination, etherification, and condensation. Three significant commercial processes for the production of amyl alcohols include separation from fusel oils, chlorination of C‐5 alkanes with subsequent hydrolysis to produce a mixture of seven of the eight isomers (Pennsalt), and a low pressure oxo process. The oxo process is the principal one in practice today. The main effects of prolonged exposure to amyl alcohols are irritation to mucous membranes and upper respiratory tract, significant depression of the central nervous system, and narcotic effects from vapor inhalation or oral absorption. All the alcohols are harmful if inhaled or swallowed. Prolonged exposure causes nausea, coughing, diarrhea, vertigo, drowsiness, headache, and vomiting. 3‐Methyl‐1‐butanol has demonstrated carcinogenic activity in animal studies. The amyl alcohols are readily flammable substances; tert ‐amyl alcohol is the most flammable. Their vapors can form explosive mixtures with air. Amyl alcohols are best stored or shipped in either aluminum, lined steel, or stainless steel tanks.

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Amyl Alcohols

Papa¹

2003

Kirk-Othmer Encyclopedia of Chemical Technology

View full text Add to dashboard Cite

Amyl alcohol describes any saturated aliphatic alcohol containing five carbon atoms. This class consists of three pentanols, four substituted butanols, and a disubstituted propanol, ie, eight structural isomers C 5 H 12 O: four primary, three secondary, and one tertiary alcohol. In addition, 2‐pentanol, 2‐methyl‐1‐butanol, and 3‐methyl‐2‐butanol have chiral centers and hence two enantiomeric forms. The odd‐carbon structure and the extent of branching provide amyl alcohols with unique physical and solubility properties and often offer ideal properties for solvent, surfactant, extraction, gasoline additive, and fragrance applications. Today the most important industrial process for amyl alcohol production is low pressure rhodium‐catalyzed hydroformylation (oxo process) of butenes. Mixtures of isomeric amyl alcohols (1‐pentanol and 2‐methyl‐1‐butanol) are often preferred because they are less expensive to produce commercially and have a more desirable combination of properties. With the exception of neopentyl alcohol (mp 53°C), the amyl alcohols are clear, colorless liquids under atmospheric conditions, with characteristic, slightly pungent and penetrating odors. Commercial primary amyl alcohol is a mixture of 1‐pentanol and 2‐methyl‐1‐butanol. Like the lower alcohols, amyl alcohols are completely miscible with numerous organic solvents and are excellent solvents for nitrocellulose, resin lacquers, higher esters, and various natural and synthetic gums and resins. However, in contrast to the lower alcohols, they are only slightly soluble in water. Important amyl alcohol reactions include dehydration, esterification, oxidation, amination, etherification, and condensation. Three significant commercial processes for the production of amyl alcohols include separation from fusel oils, chlorination of C‐5 alkanes with subsequent hydrolysis to produce a mixture of seven of the eight isomers (Pennsalt), and a low pressure oxo process. The oxo process is the principal one in practice today. The main effects of prolonged exposure to amyl alcohols are irritation to mucous membranes and upper respiratory tract, significant depression of the central nervous system, and narcotic effects from vapor inhalation or oral absorption. All the alcohols are harmful if inhaled or swallowed. 3‐Methyl‐1‐butanol has demonstrated carcinogenic activity in animal studies. The amyl alcohols are readily flammable substances; tert ‐amyl alcohol is the most flammable. Their vapors can form explosive mixtures with air. Amyl alcohols are best stored or shipped in either aluminum, lined steel, or stainless steel tanks.

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The rhodium-promoted guerbet reaction

Cited by 44 publications

References 7 publications

Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

Amyl Alcohols

Amyl Alcohols

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