Carbonylation

Organic chemistry

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. Carbonylations are the basis of two main types of reactions, hydroformylation and Reppe Chemistry.

Hydroformylation

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

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

RCHO → RH + CO

Reppe chemistry

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. 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. In the industrial synthesis of ibuprofen, a benzylic alcohol is converted to the corresponding carboxylic acid via a Pd-catalyzed carbonylation:

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:

H₂C=CH₂ + H₂O + CO → CH₃CH₂CO₂H

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

Other reactions

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:

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. 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.

Carbonylation in inorganic chemistry

Metal carbonyls, compounds with the formula M(CO)_xL_y (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. Inorganic compounds that contain CO ligands can also undergo decarbonylation, often via a photochemical reaction.

Protein carbonylation

The modification of side chains in a few native amino acids such as histidine, cysteine, and lysine in proteins to carbonyl derivatives (aldehydes and ketones) is known as protein carbonylation. Oxidative stress, often metal catalyzed, leads to protein carbonylation.