Carbonylation

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Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

Protein carbonylation[edit]

The modification of native amino acids side chains in proteins to carbonyl (aldehyde and ketone) derivatives is known as protein carbonylation.[1] Oxidative stress, often metal catalyzed, leads to protein carbonylation.

Organic chemistry[edit]

Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic carbonyls, i.e., compounds that contain the C=O functional group such as aldehydes, carboxylic acids, and esters.[2][3] Carbonylations are the basis of two main types of reactions, hydroformylation and Reppe Chemistry.

Hydroformylation[edit]

Hydroformylation entails the addition of both carbon monoxide and hydrogen to unsaturated organic compounds, usually alkenes. The usual products are aldehydes:

RCH=CH2 + H2 + CO → RCH2CH2CHO

The reaction requires metal catalysts that bind the CO, the H2, and the alkene, allowing these substrates to combine within its coordination sphere.

Decarbonylation[edit]

Many organic carbonyls undergo decarbonylation. A common transformation involves the conversion of aldehydes to alkanes, usually catalyzed by metal complexes:[4]

RCHO → RH + CO

Reppe chemistry[edit]

Reppe Chemistry, named after Walter Reppe, entails addition of carbon monoxide and an acidic hydrogen donor to the organic substrate. Large-scale applications of this type of carbonylation are the Monsanto and Cativa processes, which convert methanol to acetic acid. Acetic anhydride is prepared by a related carbonylation of methyl acetate.[5] In the related hydrocarboxylation and hydroesterification, alkenes and alkynes are the substrates. This method is used in industry to produce propionic acid from ethylene:

RCH=CH2 + H2O + CO → RCH2CH2CO2H

These reactions require metal catalysts, which bind and activate the CO.[6] In the industrial synthesis of ibuprofen, a benzylic alcohol is converted to the corresponding carboxylic acid via a Pd-catalyzed carbonylation:[2]

ArCH(CH3)OH + CO → ArCH(CH3)CO2H

Acrylic acid was once prepared by the hydrocarboxylation of acetylene but is now produced by the oxidation of propene. The hydrocarboxylation of alkenes is a prominent example of Reppe chemistry. In industry, propanoic acid is mainly produced by the hydrocarboxylation of ethylene using nickel carbonyl as the catalyst:[7]

H2C=CH2 + H2O + CO → CH3CH2CO2H

Hydroesterification is like hydrocarboxylation, but uses alcohols instead of water.[8]

Other reactions[edit]

The Koch reaction (also the related Koch-Haaf reactions) entail the addition of CO to unsaturated compounds in the presence of strong acids such as sulfuric acid. This method is less frequently used in industry as are the metal-catalyzed reactions, described above. The industrial synthesis of glycolic acid is achieved in this way:[9]

CH2O + CO + H2O → HOCH2CO2H

The conversion of isobutene to pivalic acid is also illustrative:

(CH3)2C=CH2 + H2O + CO → (CH3)3CCO2H

Unrelated to the Koch reaction, dimethyl carbonate and dimethyl oxalate are also produced in industry from carbon monoxide.[2] These reactions require oxidants:

2 CH3OH + 1/2 O2 + CO → (CH3O)2CO + H2O

Alkyl, benzyl, vinyl, aryl, and allyl halides can also be carbonylated in the presence carbon monoxide and suitable catalysts such as manganese, iron, or nickel powders.[10]

Carbonylation in inorganic chemistry[edit]

Main article: metal carbonyl

Metal carbonyls, compounds with the formula M(CO)xLy (M = metal; L = other ligands) are prepared by carbonylation of transition metals. Iron and nickel powder react directly with CO to give Fe(CO)5 and Ni(CO)4, respectively. Most other metals form carbonyls less directly, such as from their oxides or halides. Metal carbonyls are widely employed as catalysts in the hydroformylation and Reppe processes discussed above.[11] Inorganic compounds that contain CO ligands can also undergo decarbonylation, often via a photochemical reaction.

References[edit]

  1. ^ Dalle-Donne, Isabella; Aldini, Giancarlo; Carini, Marina; Colombo, Roberto; Rossi, Ranieri; Milzani, Aldo (2006). "Protein carbonylation, cellular dysfunction, and disease progression". Journal of Cellular and Molecular Medicine 10 (2): 389–406. doi:10.1111/j.1582-4934.2006.tb00407.x. PMID 16796807.  Grimsrud, P. A.; Xie, H.; Griffin, T. J.; Bernlohr, D. A. (2008). "Oxidative Stress and Covalent Modification of Protein with Bioactive Aldehydes". Journal of Biological Chemistry 283 (32): 21837–41. doi:10.1074/jbc.R700019200. PMC 2494933. PMID 18445586. 
  2. ^ a b c Bertleff, Werner (2000). "Carbonylation". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a05_217. ISBN 3527306730. 
  3. ^ Arpe, .J.: Industrielle organische Chemie: Bedeutende vor- und Zwischenprodukte, 2007, Wiley-VCH-Verlag, ISBN 3-527-31540-3
  4. ^ Hartwig, J. F. Organotransition Metal Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010.
  5. ^ Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. (1992). "Eastman Chemical Company Acetic Anhydride Process". Catalysis Today 13: 73–91. doi:10.1016/0920-5861(92)80188-S. 
  6. ^ Beller, Matthias; Cornils, B.; Frohning, C. D.; Kohlpaintner, C. W. (1995). "Progress in hydroformylation and carbonylation". Journal of Molecular Catalysis A 104: 17–85. doi:10.1016/1381-1169(95)00130-1. 
  7. ^ W. Bertleff; M. Roeper; X. Sava (2005), "Carbonylation", Ullmann's Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, doi:10.1002/14356007.a05_217 
  8. ^ El Ali, B.; Alper, H. "Hydrocarboxylation and hydroesterification reactions catalyzed by transition metal complexes" In Transition Metals for Organic Synthesis, 2nd ed.; Beller, M., Bolm, C., Eds.; Wiley-VCH:Weinheim, 2004. ISBN 978-3-527-30613-8
  9. ^ Karlheinz Miltenberger, "Hydroxycarboxylic Acids, Aliphatic" in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH: Weinheim, 2003.
  10. ^ Riemenschneider, Wilhelm; and Bolt, Hermann (2000). "Esters, Organic". Ullmann's Encyclopedia of Industrial Chemistry: 10. doi:10.1002/14356007.a09_565. Retrieved 17 December 2013. 
  11. ^ Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2