In
organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
, a ketene is an
organic compound
In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...
of the form , where R and R' are two arbitrary
monovalent chemical groups (or two separate
substitution sites in the same molecule).
The name may also refer to the specific compound
ethenone
In organic chemistry, ethenone is the formal name for ketene, an organic compound with formula or . It is the simplest member of the ketene class. It is an important reagent for acetylations.
Properties
Ethenone is a highly reactive gas (at ...
, the simplest ketene.
Although they are highly useful, most ketenes are
unstable
In numerous fields of study, the component of instability within a system is generally characterized by some of the outputs or internal states growing without bounds. Not all systems that are not stable are unstable; systems can also be mar ...
. When used as
reagents in a chemical procedure, they are typically generated when needed, and consumed as soon as (or while) they are produced.
History
Ketenes were first studied as a class by
Hermann Staudinger before 1905.
Ketenes were systematically investigated by Hermann Staudinger in 1905 in the form of diphenylketene (conversion of
-chlorodiphenyl acetyl chloride with zinc). Staudinger was inspired by the first examples of reactive organic intermediates and stable radicals discovered by
Moses Gomberg
Moses Gomberg (February 8, 1866 – February 12, 1947) was a chemistry professor at the University of Michigan. He was elected to the National Academy of Sciences and served as president of the American Chemical Society.
Early life and education
...
in 1900 (compounds with triphenylmethyl group).
Properties
Ketenes are highly electrophilic at the carbon atom bonded with the heteroatom, due to its ''sp'' character. Ketene can be formed with different heteroatom bonded to the ''sp'' carbon atom, such as
O,
S or
Se, respectively named ketene,
thioketene
In organic chemistry, thioketenes are organosulfur compounds analogous to ketenes with the general formula , where R is alkyl or aryl. Thioketene (ethenthione) is also the name of the compound , which is the simplest thioketene. Thioketenes are ...
and
selenoketene.
Ethenone
In organic chemistry, ethenone is the formal name for ketene, an organic compound with formula or . It is the simplest member of the ketene class. It is an important reagent for acetylations.
Properties
Ethenone is a highly reactive gas (at ...
, the simplest ketene, has different experimental lengths for each of the double bonds; the C=O bond is 1,160
Å and the C=C bond is 1,314Å. The angle between the two
H atoms is 121.5°, similar to the theoretically ideal angle formed in
alkenes
In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.
Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...
between ''sp
2 ''carbon atom and H substituents.
Ketenes are unstable and cannot be stored. In the absence of nucleophiles with which to react, ethenone dimerises to give β-
lactone
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring.
Lactones are formed by intramolecular esterification of the co ...
, a cyclic
ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
. If the ketene is disubstituted, the dimerisation product is a substituted cyclobutadione. For monosubstituted ketenes, the dimerisation could afford either the ester or the diketone product.
Synthesis
Ethenone can be generated by
pyrolysis
The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
(thermal cracking) of
acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
:
:CH
3−CO−CH
3 → CH
2=C=O + CH
4
This reaction is called the Schmidlin ketene synthesis.
Other ketenes can be prepared from
acyl chlorides by an
elimination reaction
An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one- or two-step mechanism. The one-step mechanism is known as the E2 reaction, and the two-step mechanism is known as the E1 r ...
in which
HCl HCL may refer to:
Science and medicine
* Hairy cell leukemia, an uncommon and slowly progressing B cell leukemia
* Harvard Cyclotron Laboratory, from 1961 to 2002, a proton accelerator used for research and development
* Hollow-cathode lamp, a spe ...
is lost:
:
In this reaction, a base, usually
triethylamine
Triethylamine is the chemical compound with the formula N(CH2CH3)3, commonly abbreviated Et3N. It is also abbreviated TEA, yet this abbreviation must be used carefully to avoid confusion with triethanolamine or tetraethylammonium, for which TEA ...
, removes the
acid
In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
ic
proton
A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
alpha to the
carbonyl
In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups. A compound containing a ...
group, inducing the formation of the carbon-carbon double bond and the loss of a
chloride
The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...
ion:
Ketenes can also be formed from α-
diazoketones by
Wolff rearrangement
The Wolff rearrangement is a reaction in organic chemistry in which an α-diazocarbonyl compound is converted into a ketene by loss of dinitrogen with accompanying 1,2-rearrangement. The Wolff rearrangement yields a ketene as an intermediate produ ...
.
Another way to generate ketenes is through
flash vacuum thermolysis
The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
(FVT) with 2-
pyridylamines. Plüg and Wentrup developed a method in 1997 that improved on FVT reactions to produce ketenes with a stable FVT that is moisture insensitive, using mild conditions (480 °C). The N-pyridylamines are prepared via a condensation with R-
malonate
The conjugate acids are in :Carboxylic acids.
{{Commons category, Carboxylate ions, Carboxylate anions
Carbon compounds
Oxyanions ...
s with N-amino(
pyridene) and
DCC as the solvent.
A more robust method for preparing ketenes is the
carbonylation
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 carbony ...
of
metal-carbenes, and ''in situ'' reaction of the thus produced highly reactive ketenes with suitable reagents such as
imines
In organic chemistry, an imine ( or ) is a functional group or organic compound containing a carbon–nitrogen double bond (). The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bon ...
,
amines
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent such ...
, or
alcohols
In chemistry, an alcohol is a type of organic compound that carries at least one hydroxyl () functional group bound to a saturated carbon atom. The term ''alcohol'' originally referred to the primary alcohol ethanol (ethyl alcohol), which is ...
. This method is an efficient
one‐pot tandem protocol of the carbonylation of α‐diazocarbonyl compounds and a variety of ''N''‐tosylhydrazones catalysed by Co(II)–
porphyrin
Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical com ...
metalloradicals leading to the formation of ketenes, which subsequently react with a variety of
nucleophile
In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...
s and imines to form
esters
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides are ...
,
amides
In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula , where R, R', and R″ represent organic groups or hydrogen atoms. The amide group is called a peptide bond when it is ...
and
β‐lactams. This system has a broad substrate scope and can be applied to various combinations of
carbene
In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is or where the R represents substituents or hydrogen atoms.
The term "carbene" ma ...
precursors, nucleophiles and imines.
Reactions and applications
Due to their
cumulated double bonds, ketenes are very reactive.
Formation of carboxylic acid esters
By reaction with alcohols,
carboxylic acid esters are formed:
:
Formation of carboxylic anhydrides
Ketenes react with a carboxylic acids to form
carboxylic acid anhydride
An organic acid anhydride is an acid anhydride that is an organic compound. An acid anhydride is a compound that has two acyl groups bonded to the same oxygen atom. A common type of organic acid anhydride is a carboxylic anhydride, where the pa ...
s:
:
Formation of carboxylic acid amides
Ketenes react with
ammonia
Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
to
primary amides:
:
The reaction of ketenes with
primary amine
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent such ...
s produces
secondary amides:
:
Ketenes react with
secondary amine
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent such ...
s to give tertiary amides:
:
Hydrolysis
By reaction with water, carboxylic acids are formed from ketenes
:
Formation of enol esters
Enol esters are formed from ketenes with
enol
In organic chemistry, alkenols (shortened to enols) are a type of reactive structure or intermediate in organic chemistry that is represented as an alkene ( olefin) with a hydroxyl group attached to one end of the alkene double bond (). The t ...
isable
carbonyl compounds
In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups. A compound containing a ...
. The following example shows the reaction of
ethenone
In organic chemistry, ethenone is the formal name for ketene, an organic compound with formula or . It is the simplest member of the ketene class. It is an important reagent for acetylations.
Properties
Ethenone is a highly reactive gas (at ...
with
acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
to form a propen-2-yl acetate:
:
Dimerisation
At room temperature, ketene quickly dimerizes to
diketene
Diketene is an organic compound with the molecular formula , and which is sometimes written as . It is formed by dimerization of ketene, . Diketene is a member of the oxetane family. It is used as a reagent in organic chemistry. It is a colorles ...
, but the ketene can be recovered by heating:
:
+2cycloaddition
Ketenes can react with
alkenes
In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond.
Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...
, carbonyl compounds,
carbodiimides
In organic chemistry, a carbodiimide (systematic IUPAC name: methanediimine) is a functional group with the formula RN=C=NR. They are exclusively synthetic. A well known carbodiimide is dicyclohexylcarbodiimide, which is used in peptide synthesis. ...
and imines in a
cycloaddition">+2cycloaddition. The example shows the synthesis of a
β-lactam
A beta-lactam (β-lactam) ring is a four-membered lactam. A ''lactam'' is a cyclic amide, and ''beta''-lactams are named so because the nitrogen atom is attached to the β-carbon atom relative to the carbonyl. The simplest β-lactam possible is ...
by the reaction of a ketene with an imine (see
Staudinger synthesis
The Staudinger synthesis, also called the Staudinger ketene-imine cycloaddition, is a chemical synthesis in which an imine 1 reacts with a ketene 2 through a non-photochemical 2+2 cycloaddition to produce a ''β''-lactam 3. The reaction carries ...
):
:
Applications
Ketenes are generally very reactive, and participate in various
cycloaddition
In organic chemistry, a cycloaddition is a chemical reaction in which "two or more unsaturated molecules (or parts of the same molecule) combine with the formation of a cyclic adduct in which there is a net reduction of the bond multiplicity". T ...
s. One important process is the dimerization to give
propiolactones. A specific example is the dimerization of the ketene of
stearic acid
Stearic acid ( , ) is a saturated fatty acid with an 18-carbon chain. The IUPAC name is octadecanoic acid. It is a waxy solid and its chemical formula is C17H35CO2H. Its name comes from the Greek word στέαρ "''stéar''", which means tallow. ...
to afford
alkyl ketene dimers, which are widely used in the paper industry.
AKD's react with the hydroxyl groups on the cellulose via
esterification
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
reaction.
They will also undergo
+2cycloaddition reactions with electron-rich
alkynes to form
cyclobutenones, or carbonyl groups to form beta-
lactone
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring.
Lactones are formed by intramolecular esterification of the co ...
s. With
imine
In organic chemistry, an imine ( or ) is a functional group or organic compound containing a carbon–nitrogen double bond (). The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bo ...
s, beta-lactams are formed. This is the Staudinger synthesis, a facile route to this important class of compounds. With
acetone
Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour.
Acetone is miscib ...
, ketene reacts to give
isopropenyl acetate.
A variety of
hydroxylic
In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydro ...
compounds can add as nucleophiles, forming either
enol
In organic chemistry, alkenols (shortened to enols) are a type of reactive structure or intermediate in organic chemistry that is represented as an alkene ( olefin) with a hydroxyl group attached to one end of the alkene double bond (). The t ...
or
ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ar ...
products. As examples, a water molecule easily adds to ketene to give
1,1-dihydroxyethene and
acetic anhydride is produced by the reaction of
acetic acid
Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...
with ketene. Reactions between
diols () and bis-ketenes () yield
polyester
Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include natural ...
s with a repeat unit of ().
Ethyl acetoacetate
The organic compound ethyl acetoacetate (EAA) is the ethyl ester of acetoacetic acid. It is a colorless liquid. It is widely used as a chemical intermediate in the production of a wide variety of compounds. It is used as a flavoring for food.
...
, an important starting material in organic synthesis, can be prepared using a
diketene
Diketene is an organic compound with the molecular formula , and which is sometimes written as . It is formed by dimerization of ketene, . Diketene is a member of the oxetane family. It is used as a reagent in organic chemistry. It is a colorles ...
in reaction with
ethanol
Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an Alcohol (chemistry), alcohol with the chemical formula . Its formula can be also written as or (an ethyl ...
. They directly form ethyl acetoacetate, and the yield is high when carried out under controlled circumstances; this method is therefore used industrially.
See also
*
Ynol
In organic chemistry, an alkynol (shortened to ynol) is an alkyne with a hydroxyl group affixed to one of the two carbon atoms composing the triple bond (). The deprotonated anions of ynols are known as '' ynolates''. An ynol with hydroxyl gro ...
*
Thioketene
In organic chemistry, thioketenes are organosulfur compounds analogous to ketenes with the general formula , where R is alkyl or aryl. Thioketene (ethenthione) is also the name of the compound , which is the simplest thioketene. Thioketenes are ...
References
External links
*
{{Authority control
Functional groups