Carbonylation

Carbonylation refers to

reaction

s 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.

Organic chemistry

Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic

carbonyl

s, i.e., compounds that contain the C=O functional group such as

aldehyde

s, carboxylic acids, and

ester

s. Carbonylations are the basis of many types of reactions, including hydroformylation and Reppe Chemistry. These reactions require metal catalysts, which bind and activate the CO. Much of this theme was developed by

Walter Reppe

.

Hydroformylation

Hydroformylation

entails the addition of both carbon monoxide and

hydrogen

to unsaturated organic compounds, usually

alkenes

. The usual products are

aldehyde

s:
:RCH=CH₂ + H₂ + CO → RCH₂CH₂CHO
The reaction requires metal

catalyst

s that bind CO, forming intermediate metal carbonyls. Many of the commodity carboxylic acids, i.e. propionic, butyric, valeric, etc, as well as many of the commodity alcohols, i.e. propanol, butanol, amyl alcohol, are derived from aldehydes produced by hydroformylation. In this way, hydroformylation is a gateway from alkenes to oxygenates.

Decarbonylation

Many organic carbonyls undergo

decarbonylation

. A common transformation involves the conversion of aldehydes to alkanes, usually catalyzed by metal complexes:
:RCHO → RH + CO
Few catalysts are highly active or exhibit broad scope.Kreis, M.; Palmelund, A.; Bunch, L.; Madsen, R., "A General and Convenient Method for the Rhodium-Catalyzed Decarbonylation of Aldehydes", Advanced Synthesis & Catalysis 2006, 348, 2148-2154.

Acetic acid and acetic anhydride

Large-scale applications of carbonylation are the Monsanto and Cativa processes, which convert methanol to acetic acid. In another major industrial process, Acetic anhydride is prepared by a related carbonylation of methyl acetate.

Oxidative carbonylation

Dimethyl carbonate and dimethyl oxalate are produced industrially using carbon monoxide and an oxidant, in effect as a source of CO²⁺.
:2 CH₃OH + 1/2 O₂ + CO → (CH₃O)₂CO + H₂O
The oxidative carbonylation of methanol is catalyzed by copper(I) salts, which form transient carbonyl complexes. For the oxidative carbonylation of alkenes, palladium complexes are used.

Hydrocarboxylation and hydroesterification

In hydrocarboxylation, alkenes and alkynes are the substrates. This method is used industrially to produce

propionic acid

from ethylene using

nickel carbonyl

as the catalyst:
:RCH=CH₂ + H₂O + CO → RCH₂CH₂CO₂H
In the industrial synthesis of

ibuprofen

, a

benzyl

ic alcohol is converted to the corresponding arylacetic acid via a Pd-catalyzed carbonylation:
:ArCH(CH₃)OH + CO → ArCH(CH₃)CO₂H

Acrylic acid

was once mainly prepared by the hydrocarboxylation of acetylene.
:
Nowadays, however, the preferred route to acrylic acid entails the oxidation of propene, exploiting its low cost and the high reactivity of the

allyl

ic C-H bonds.

Hydroesterification is like hydrocarboxylation, but it uses alcohols in place of water. This reaction is employed for the production of

methyl propionate

from ethylene:
:C₂H₄ + CO + MeOH → CH₃CH₂CO₂Me
The process is catalyzed by Herrmann's catalyst, Pd ₆H₄(CH₂PBu-t)₂sub>2. Under similar conditions, other Pd-diphosphines catalyze formation of

polyethyleneketone

.

Other reactions

The

Koch reaction

is a special case of hydrocarboxylation reaction that does not rely on metal catalysts. Instead, the process is catalyzed by strong acids such as

sulfuric acid

or the combination of

phosphoric acid

and boron trifluoride. The reaction is less applicable to simple alkene. 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:
:Me₂C=CH₂ + H₂O + CO → Me₃CCO₂H

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.Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim. {{ISBN, 978-3-527-29390-2 Inorganic compounds that contain CO ligands can also undergo decarbonylation, often via a photochemical reaction.

References

Chemical reactions
Carbon monoxide