Ketene

General formula for a ketene.

A ketene is an organic compound of the form R′R″C=C=O. The term is also used specifically to mean ethenone, the simplest ketene, where R′ and R″ are hydrogen atoms.

Ketenes were first studied as a class by Hermann Staudinger.^[1]

Formation

Ethenone, the simplest ketene, can be formed by pyrolysis (thermal cracking) of acetone:

CH₃−CO−CH₃ + ΔT → CH₂=C=O + CH₄

This reaction is called the Schmidlin ketene synthesis.^[2][3]

Ketenes can be prepared from acyl chlorides by an elimination reaction in which HCl is lost:

In this reaction, a base, usually triethylamine, removes the acidic proton alpha to the carbonyl group, inducing the formation of the carbon-carbon double bond and the loss of a chloride ion.

Ketenes can also be formed from α-diazoketones by Wolff rearrangement.

Another way to generate ketenes is through flash vacuum thermolysis with 2-pyridylamines. Plug and Werdup 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-malonates with N-amino(pyridene) and DCC as the solvent.^[4]

Reactions

Ketenes are generally very reactive, and participate in various cycloadditions. They will also undergo [2+2] cycloaddition reactions with electron-rich alkynes to form cyclobutenones, or carbonyl groups to form beta-lactones. With imines beta-lactams are formed. This is the Staudinger synthesis, a facile route to this important class of compounds. With acetone, ketene reacts to give Isopropenyl acetate.

Reactions between diols (HO−R−OH) and bis-ketenes (O=C=CH−R′−CH=C=O) yield polyesters with a repeat unit of (−O−R−O−CO−R′−CO).

Ethyl acetoacetate, a very important starting material in organic synthesis, can be prepared using a diketene in reaction with ethanol. They directly form ethyl acetoacetate, and the yield is high when carried out under controlled circumstances; this method is therefore used industrially.

See also

• Ynolate
• Thioketene

References

Molecules detected in outer space
Molecules	Diatomic Aluminium monochloride Aluminium monofluoride Aluminium monoxide Argonium Carbon monophosphide Carbon monosulfide Carbon monoxide Carborundum Cyanogen radical Diatomic carbon Fluoromethylidynium Hydrogen chloride Hydrogen fluoride Hydrogen (molecular) Hydroxyl radical Iron(II) oxide Magnesium monohydride cation Methylidyne radical Nitric oxide Nitrogen (molecular) Nitrogen monohydride Nitrogen sulfide Oxygen (molecular) Phosphorus monoxide Phosphorus mononitride Potassium chloride Silicon carbide Silicon mononitride Silicon monoxide Silicon monosulfide Sodium chloride Sodium iodide Sulfur monohydride Sulfur monoxide Titanium oxide Triatomic Aluminium hydroxide Aluminium isocyanide Amino radical Carbon dioxide Carbonyl sulfide CCP radical Chloronium Diazenylium Dicarbon monoxide Disilicon carbide Ethynyl radical Formyl radical Hydrogen cyanide (HCN) Hydrogen isocyanide (HNC) Hydrogen sulfide Hydroperoxyl Iron cyanide Isoformyl Magnesium cyanide Magnesium isocyanide Methylene radical N2H+ Nitrous oxide Nitroxyl Ozone Phosphaethyne Potassium cyanide Protonated molecular hydrogen Sodium cyanide Sodium hydroxide Silicon carbonitride c-Silicon dicarbide Silicon naphthalocyanine Sulfur dioxide Thioformyl Thioxoethenylidene Titanium dioxide Tricarbon Water Four atoms Acetylene Ammonia Cyanic acid Cyanoethynyl Cyclopropynylidyne Formaldehyde Fulminic acid HCCN Hydrogen peroxide Hydromagnesium isocyanide Isocyanic acid Isothiocyanic acid Ketenyl Methylene amidogen Methyl radical Propynylidyne Protonated carbon dioxide Protonated hydrogen cyanide Silicon tricarbide Thioformaldehyde Tricarbon monoxide Tricarbon sulfide Thiocyanic acid Five atoms Ammonium ion Butadiynyl Carbodiimide Cyanamide Cyanoacetylene Cyanoformaldehyde Cyanomethyl Cyclopropenylidene Formic acid Isocyanoacetylene Ketene Methane Methoxy radical Methylenimine Propadienylidene Protonated formaldehyde Protonated formaldehyde Silane Silicon-carbide cluster Six atoms Acetonitrile Cyanobutadiynyl radical E-Cyanomethanimine Cyclopropenone Diacetylene Ethylene Formamide HC4N Ketenimine Methanethiol Methanol Methyl isocyanide Pentynylidyne Propynal Protonated cyanoacetylene Seven atoms Acetaldehyde Acrylonitrile Cyanodiacetylene Ethylene oxide Hexatriynyl radical Methylacetylene Methylamine Methyl isocyanate Vinyl alcohol Eight atoms Acetic acid Aminoacetonitrile Cyanoallene Ethanimine Glycolaldehyde Heptatrienyl radical Hexapentaenylidene Methylcyanoacetylene Methyl formate Propenal Nine atoms Acetamide Cyanohexatriyne Cyanotriacetylene Dimethyl ether Ethanol Methyldiacetylene Octatetraynyl radical Propene Propionitrile Ten atoms or more Acetone Benzene Buckminsterfullerene (C60 fullerene, buckyball) C70 fullerene Cyanodecapentayne Cyanopentaacetylene Cyanotetra-acetylene Ethylene glycol Ethyl formate Methyl acetate Methyl-cyano-diacetylene Methyltriacetylene Propanal n-Propyl cyanide Pyrimidine
Deuterated molecules	Ammonia Ammonium ion Formaldehyde Formyl radical Heavy water Hydrogen cyanide Hydrogen deuteride Hydrogen isocyanide Methylacetylene N2D+ Trihydrogen cation
Unconfirmed	Anthracene Dihydroxyacetone Ethyl methyl ether Glycine Graphene H2NCO+ Linear C5 Naphthalene cation Phosphine Pyrene Silylidine
Related	Abiogenesis Astrobiology Astrochemistry Atomic and molecular astrophysics Chemical formula Circumstellar envelope Cosmic dust Cosmic ray Cosmochemistry Diffuse interstellar band Extraterrestrial life Extraterrestrial liquid water Forbidden mechanism Helium hydride ion Homochirality Intergalactic dust Interplanetary medium Interstellar medium Iron–sulfur world theory Kerogen Life Life timeline Molecules in stars Nature timeline Nexus for Exoplanet System Science Organic compound Outer space PAH world hypothesis Panspermia Polycyclic aromatic hydrocarbon (PAH) RNA world hypothesis Spectroscopy Tholin
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