organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

, vinylation is the process of attaching a

vinyl group In organic chemistry, a vinyl group (abbr. Vi; IUPAC name: ethenyl group) is a functional group with the formula . It is the ethylene (IUPAC name: ethene) molecule () with one fewer hydrogen atom. The name is also used for any compound contai ...

() to a substrate. Many organic compounds contain vinyl groups, so the process has attracted significant interest, especially since the reaction scope includes substituted vinyl groups. The reactions can be classified according to the source of the vinyl group.

Nucleophilic vinyl reagents

Vinyl lithium Vinyllithium is an organolithium compound with the formula LiC2H3. A colorless or white solid, it is encountered mainly as a solution in tetrahydrofuran (THF). It is a reagent in synthesis of organic compounds, especially for vinylations.. Pr ...

and vinyl magnesium bromide are sources of "", which add to

ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

s and

aldehyde In organic chemistry, an aldehyde () (lat. ''al''cohol ''dehyd''rogenatum, dehydrogenated alcohol) is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred ...

s. Vinylsiloxane and vinylboranes have also been used as sources of vinyl anion equivalents.These types of reactions require

catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...

s such as those based on

palladium Palladium is a chemical element; it has symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1802 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas (formally 2 Pallas), ...

Vinylation with alkenes

The

Heck reaction The Heck reaction (also called the Mizoroki–Heck reaction) is the chemical reaction of an unsaturated halide (or triflate) with an alkene in the presence of a base and a palladium catalyst to form a substituted alkene. It is named after T ...

couples an unsaturated

halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fl ...

with an

alkene In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins. The Internationa ...

. Base and a

palladium catalyst Palladium is a chemical element; it has symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1802 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas (formally 2 Pallas), wh ...

are required. This reaction is a way to substitute alkenes. Heck naproxen

Vinylation with acetylene

As originally 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 Un ...

, acetylene participates in a variety of metal- or base-catalyzed reaction to afford vinyl derivatives. Alcohols, thiols, and secondary amines add to acetylene to give the vinyl ethers, vinyl sulfides, and vinyl amines, respectively. : Reppe-chemnistry-vinylization

In the presence of metal catalysts,

carbon monoxide Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...

and acetylene react to give

acrylic acid Acrylic acid (IUPAC: prop-2-enoic acid) is an organic compound with the formula CH2=CHCOOH. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. This colorless liquid has ...

or acrylic esters. The net reaction is vinylation of carbon monoxide. : Reppe-chemistry-carbonmonoxide-01

Vinyl acetate

Preparing

vinyl ester 144px, Vinyl acetate, a commercially important monomer Vinyl ester refers to esters formally derived from vinyl alcohol. Commercially important examples of these monomers are vinyl acetate Vinyl acetate is an organic compound with the Chemica ...

s typically requires indirect methods because vinyl alcohol is not a suitable reagent.

Vinyl acetate Vinyl acetate is an organic compound with the Chemical formula, formula CH3CO2CH=CH2. This colorless liquid is the precursor to polyvinyl acetate, ethylene-vinyl acetate copolymers, polyvinyl alcohol, and other important industrial polymers. Prod ...

, which is available on an industrial scale, can be used to produce other vinyl esters. The process is sometimes referred to as transvinylation. Higher esters of vinyl acetate have been used in the synthesis of

vinyl formate Vinyl formate is an organic compound with the formula . It is the ester formally derived from formic acid and vinyl alcohol Vinyl alcohol, also called ethenol (IUPAC name; not ethanol) or ethylenol, is the simplest enol. With the formula , it ...

. Alternatively, vinyl ethers can be prepared from alcohols by

iridium Iridium is a chemical element; it has the symbol Ir and atomic number 77. This very hard, brittle, silvery-white transition metal of the platinum group, is considered the second-densest naturally occurring metal (after osmium) with a density ...

-catalyzed

transesterification Transesterification is the process of exchanging the organic functional group R″ of an ester with the organic group R' of an alcohol. These reactions are often catalyzed by the addition of an acid or base catalyst. Strong acids catalyze the r ...

of vinyl esters, especially the widely available

vinyl acetate Vinyl acetate is an organic compound with the Chemical formula, formula CH3CO2CH=CH2. This colorless liquid is the precursor to polyvinyl acetate, ethylene-vinyl acetate copolymers, polyvinyl alcohol, and other important industrial polymers. Prod ...

:{{cite journal, title=Iridium-catalyzed Synthesis of Vinyl Ethers from Alcohols and Vinyl Acetate, author=Tomotaka Hirabayashi , author2=Satoshi Sakaguchi , author3=Yasutaka Ishii , journal=Org. Synth., year=2005, volume=82, page=55, doi=10.15227/orgsyn.082.0055, doi-access=free :ROH + CH₂=CHOAc → ROCH=CH₂ + HOAc

References

Vinyl compounds Vinyl esters

Nucleophilic vinyl reagents

Vinylation with alkenes

Vinylation with acetylene

Vinyl acetate

See also

References