A ketene is an organic compound of the form R′R″C=C=O, where R and R' are two arbitrary monovalent chemical groups (or two separate substitution sites in the same molecule). The name may also refers to the specific compound ethenone H
2C=C=O, the simplest ketene.
Although they are highly useful, most ketenes are unstable. When used as reagents in a chemical procedure, they are typically generated when needed, and consumed as soon as (or while) they are produced.
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 in 1900 (compounds with triphenylmethyl group).
- CH3−CO−CH3 → CH2=C=O + CH4
This reaction is called the Schmidlin ketene synthesis.
Ketenes can also be formed from α-diazoketones by Wolff rearrangement.
Another way to generate ketenes is through flash vacuum thermolysis (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-malonates with N-amino(pyridene) and DCC as the solvent.
A more robust method for preparing ketenes is the carbonylation of metal-carbenes, and “in situ” reaction of the thus produced highly reactive ketenes with suitable reagents such as imines, amines, or alcohols. 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 metalloradicals leading to the formation of ketenes, which subsequently react with a variety of nucleophiles and imines to form esters, amides and β‐lactams. This system has a broad substrate scope and can be applied to various combinations of carbene precursors, nucleophiles and imines.
Reactions and applications
Due to their cumulated double bonds, ketenes are very reactive.
Formation of carboxylic anhydrides
Ketenes react with a carboxylic acids to form carboxylic acid anhydrides:
Formation of carboxylic acid amides
Ketenes react with secondary amines to give tertiary amides:
By reaction with water, carboxylic acids are formed from ketenes
Formation of enol acetates
At room temperature, ketene quickly dimerizes to diketene, but the ketene can be recovered by heating:
Ketenes can react with alkenes, carbonyl compounds, carbodiimides and imines in the [2+2] cycloaddition. The example shows the synthesis of a β-lactam by the reaction of a ketene with an imine (see Staudinger synthesis):
Ketenes are generally very reactive, and participate in various cycloadditions. One important process is the dimerization to give propiolactones. A specific example is the dimerization of the ketene of stearic acid to afford alkyl ketene dimers, which are widely used in the paper industry. AKD's react with the hydroxyl groups on the celluose via esterification reaction.
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.
A variety of hydroxylic compounds can add as nucleophiles, forming either enol or ester 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 with ketene. 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, an 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.
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