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Carbonylation refers to
reaction Reaction may refer to a process or to a response to an action, event, or exposure: Physics and chemistry *Chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformat ...

reaction
s that introduce
carbon monoxide Carbon monoxide (chemical formula CO) is a colorless, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom. It is the simplest molecule of the oxocarbon family. In ...

carbon monoxide
into
organic Organic may refer to: * Organic, of or relating to an organism, a living entity * Organic, of or relating to an anatomical organ (anatomy), organ Chemistry * Organic matter, matter that has come from a once-living organism, is capable of decay or ...
and
inorganic In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they under ...
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 In organic chemistry Organic chemistry is a branch of chemistry that studies the structure, properties and reactions of organic compounds, which contain carbon in covalent bonding.Clayden, J.; Greeves, N. and Warren, S. (2012) ''Organic Chemistr ...

carbonyl
s, i.e., compounds that contain the C=O
functional group In organic chemistry, a functional group is a substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions re ...
such as
aldehyde Chemically, an aldehyde is a compound containing a functional group In organic chemistry, a functional group is a substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same ...

aldehyde
s,
carboxylic acid A carboxylic acid is an organic acid that contains a carboxyl group (C(=O)OH) attached to an R-group. The general formula of a carboxylic acid is R−COOH or R−CO2H, with substituent, R referring to the alkyl, alkenyl, aryl, or other group. ...
s, and
ester An ester is a chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entity, molecular entities) composed of atoms from more than one chemical element, element held together by chemic ...

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 Walter Julius Reppe (29 July 1892 in Göringen – 26 July 1969 in Heidelberg) was a German chemist. He is notable for his contributions to the chemistry of acetylene. Education and career Walter Reppe began his study of the natural sciences ...

Walter Reppe
.


Hydroformylation

Hydroformylation Hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the production of aldehydes from alkenes. This chemical reaction entails the net addition of a formyl group (CHO) and a hydrogen atom to a carbon-carbon do ...

Hydroformylation
entails the addition of both carbon monoxide and
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the che ...

hydrogen
to unsaturated organic compounds, usually
alkenes In chemistry Chemistry is the scientific Science () is a systematic enterprise that builds and organizes knowledge Knowledge is a familiarity or awareness, of someone or something, such as facts A fact is an occurrence ...

alkenes
. The usual products are
aldehyde Chemically, an aldehyde is a compound containing a functional group In organic chemistry, a functional group is a substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same ...

aldehyde
s: :RCH=CH2 + H2 + CO → RCH2CH2CHO The reaction requires metal
catalyst Catalysis () is the process of increasing the rate of a chemical reaction A chemical reaction is a process that leads to the chemical transformation of one set of chemical substance A chemical substance is a form of matter In cla ...

catalyst
s that bind CO, forming intermediate
metal carbonyl Metal carbonyls are coordination complex A coordination complex consists of a central atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up ...
s. 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
decarbonylationDecarbonylation is a type of organic reaction that involves loss of CO. It is often an undesirable reaction since it represents a degradation. In the chemistry of metal carbonyls, decarbonylation describes a substitution process, whereby a CO ligan ...

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 The Monsanto Company () was an American agrochemical An agrochemical or agrichemical, a contraction of ''agricultural chemical'', is a chemical A chemical substance is a form of matter having constant chemical composition and characteris ...
and
Cativa process 200px, Space-filling model of the [Ir(CO)2I2sup>− catalyst used in the Cativa process The Cativa process is a method for the production of acetic acid by the carbonylation of methanol. The technology, which is similar to the Monsanto process, wa ...
es, 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 Dimethyl oxalate is the organic compound with the formula (CO2CH3)2. It is the methyl group, dimethyl ester of oxalic acid. Dimethyl oxalate is a colorless or white solid that is soluble in water. Production Dimethyl oxalate can be obtained by ...
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 In organic chemistry, an alkyne is an Saturated and unsaturated compounds, unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and no other functional groups form a ...
are the substrates. This method is used industrially to produce
propionic acid Propionic acid (, from the Greek#REDIRECT Greek Greek may refer to: Greece Anything of, from, or related to Greece Greece ( el, Ελλάδα, , ), officially the Hellenic Republic, is a country located in Southeast Europe. Its population ...

propionic acid
from ethylene using
nickel carbonyl Nickel carbonyl (IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering OrganizationsNational Adhering Organizations in chemistry are the organizations that work as the authori ...

nickel carbonyl
as the catalyst: :RCH=CH2 + H2O + CO → RCH2CH2CO2H In the industrial synthesis of
ibuprofen Ibuprofen is a medication in the nonsteroidal anti-inflammatory drug (NSAID) class that is used for treating pain, fever, and inflammation. This includes dysmenorrhea, painful menstrual periods, migraines, and rheumatoid arthritis. It may also ...

ibuprofen
, a
benzyl In organic chemistry Organic chemistry is a branch of chemistry Chemistry is the study of the properties and behavior of . It is a that covers the that make up matter to the composed of s, s and s: their composition, structure, prop ...

benzyl
ic alcohol is converted to the corresponding arylacetic acid via a Pd-catalyzed carbonylation: :ArCH(CH3)OH + CO → ArCH(CH3)CO2H
Acrylic acid Acrylic acid (IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations that represents chemists in individual countries. It is a member of the International Science ...

Acrylic acid
was once mainly prepared by the hydrocarboxylation of acetylene. : Nowadays, however, the preferred route to acrylic acid entails the oxidation of
propene Propene, also known as propylene, is an unsaturated organic compound In , organic compounds are generally any s that contain - . Due to carbon's ability to (form chains with other carbon s), millions of organic compounds are known. The s ...
, exploiting its low cost and the high reactivity of the
allyl An allyl group is a substituent with the structural formula H2C=CH−CH2R, where R is the rest of the molecule. It consists of a methylene bridge (−CH2−) attached to a vinyl group (−CH=CH2). The name is derived from the Latin word for garlic, ...

allyl
ic C-H bonds.
HydroesterificationIn industrial chemistry, carboalkoxylation is a process for converting alkenes to esters. Also called hydroesterification, this reaction is a form of carbonylation. A closely related reaction is hydrocarboxylation, which employs water in place of a ...
is like hydrocarboxylation, but it uses alcohols in place of water. This reaction is employed for the production of
methyl propionate Methyl propionate, also known as methyl propanoate, is the organic compound , CH4; is among the simplest organic compounds. In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen chemical bond, bonds. D ...

methyl propionate
from ethylene: :C2H4 + CO + MeOH → CH3CH2CO2Me The process is catalyzed by
Herrmann's catalyst Herrmann's catalyst is an organopalladium compound that is a popular catalyst for the Heck reaction. It is a yellow air-stable solid that is soluble in organic solvents. Under conditions for catalysis, the acetate group is lost and the Pd-C bond ...
, Pd 6H4(CH2PBu-t)2sub>2. Under similar conditions, other Pd-diphosphines catalyze formation of .


Other reactions

The
Koch reaction The Koch reaction is an organic reaction for the synthesis of tertiary carboxylic acids from alcohols or alkenes. The chemical reaction, reaction is a strongly acid-catalysis, catalyzed carbonylation using carbon monoxide, and typically occurs at ...

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 Sulfuric acid (American spelling Despite the various English dialects spoken from country to country and within different regions of the same country, there are only slight regional variations in English orthography English orthogra ...

sulfuric acid
or the combination of
phosphoric acid Phosphoric acid, also known as orthophosphoric acid or phosphoric(V) acid, is a weak acid with the chemical formula . The pure compound is a colorless solid. All three hydrogens are acidic to varying degrees and can be lost from the molecule ...

phosphoric acid
and
boron trifluoride Boron trifluoride is the inorganic compound with the chemical formula, formula BF3. This pungent colourless toxic gas forms white fumes in moist air. It is a useful Lewis acid and a versatile building block for other boron compounds. Structure ...
. The reaction is less applicable to simple alkene. The industrial synthesis of
glycolic acid Glycolic acid (hydroxyacetic acid, or hydroacetic acid); chemical formula C2H4O3 (also written as HOCH2CO2H), is the smallest α-hydroxy acid (AHA). This colorless, odorless, and hygroscopic Hygroscopy is the phenomenon of attracting and hold ...

glycolic acid
is achieved in this way: :CH2O + CO + H2O → HOCH2CO2H The conversion of
isobutene Isobutylene (or 2-methylpropene) is a hydrocarbon In organic chemistry Organic chemistry is a branch of chemistry Chemistry is the study of the properties and behavior of . It is a that covers the that make up matter to the compos ...

isobutene
to
pivalic acid Pivalic acid is a carboxylic acid A carboxylic acid is an organic acid that contains a carboxyl group (C(=O)OH) attached to an R-group. The general formula of a carboxylic acid is R−COOH or R−CO2H, with R referring to the alkyl, alken ...

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 Manganese is a chemical element In chemistry, an element is a pure Chemical substance, substance consisting only of atoms that all have the same numbers of protons in their atomic nucleus, nuclei. Unlike chemical compounds, chemical e ...

manganese
,
iron Iron () is a chemical element In chemistry Chemistry is the study of the properties and behavior of . It is a that covers the that make up matter to the composed of s, s and s: their composition, structure, properties, behav ...

iron
, or
nickel Nickel is a chemical element In chemistry, an element is a pure Chemical substance, substance consisting only of atoms that all have the same numbers of protons in their atomic nucleus, nuclei. Unlike chemical compounds, chemical elem ...

nickel
powders.


Carbonylation in inorganic chemistry

Metal carbonyl Metal carbonyls are coordination complex A coordination complex consists of a central atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up ...
s, compounds with the formula M(CO)xLy (M = metal; L = other
ligand In coordination chemistry A coordination complex consists of a central atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by havi ...
s) 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 reactionOrganic photochemistry encompasses organic reactions that are induced by the action of light. The absorption of ultraviolet light by organic molecules often leads to reactions. In the earliest days, sunlight was employed, while in more modern times u ...
.


References

Chemical reactions Carbon monoxide