Vinyl alcohol

Last updated
Vinyl alcohol
Structural formula of ethenol Ethenol-2D.png
Structural formula of ethenol
Ball-and-stick model of ethenol Ethenol-3D-balls.png
Ball-and-stick model of ethenol
Names
Preferred IUPAC name
Ethenol
Other names
Hydroxyethene
Hydroxyethylene
Ethylenol
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.008.350 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C2H4O/c1-2-3/h2-3H,1H2 Yes check.svgY
    Key: IMROMDMJAWUWLK-UHFFFAOYSA-N Yes check.svgY
  • InChI=1S/C2H4O/c1-2-3/h2-3H,1H2
  • InChI=1S/C2H4O/c1-2-3/h2-3H,1H2
    Key: IMROMDMJAWUWLK-UHFFFAOYSA-N
  • OC=C
Properties
C2H4O
Molar mass 44.053 g/mol
Related compounds
Related compounds
Allyl alcohol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Vinyl alcohol, also called ethenol (IUPAC name; not ethanol) or ethylenol, is the simplest enol. With the formula C H 2CHOH, it is a labile compound that converts to acetaldehyde immediately upon isolation near room temperature. [1] It is not a practical precursor to any compound.

Contents

Synthesis

Vinyl alcohol can be formed by the pyrolytic elimination of water from ethylene glycol at a temperature of 900 °C and low pressure. [2]

Tautomerization of vinyl alcohol to acetaldehyde

Under normal conditions, vinyl alcohol converts (tautomerizes) to acetaldehyde:

Ethenol-ethanal tautomerisation.svg

At room temperature, acetaldehyde (H3CC(O)H) is more stable than vinyl alcohol (H2C=CHOH) by 42.7 kJ/mol. [3] Vinyl alcohol gas isomerizes to the aldehyde with a half-life of 30 min at room temperature.. [1]

H2C=CHOH → H3CC(O)H
The industrial synthesis of acetaldehyde (Wacker process) proceeds via the intermediacy of a vinyl alcohol complex. WackerCycleKeith&HenryImp.png
The industrial synthesis of acetaldehyde (Wacker process) proceeds via the intermediacy of a vinyl alcohol complex.

The uncatalyzed keto–enol tautomerism by a 1,3-hydrogen migration is forbidden by the Woodward–Hoffmann rules and therefore has a high activation barrier and is not a significant pathway at or near room temperature. However, even trace amounts of acids or bases (including water) can catalyze the reaction. Even with rigorous precautions to minimize adventitious moisture or proton sources, vinyl alcohol can only be stored for minutes to hours before it isomerizes to acetaldehyde. (Carbonic acid is another example of a substance that is stable when rigorously pure, but decomposes rapidly due to catalysis by trace moisture.)

The tautomerization can also be catalyzed via photochemical process. These findings suggest that the keto–enol tautomerization is a viable route under atmospheric and stratospheric conditions, relevant to a role for vinyl alcohol in the production of organic acids in the atmosphere. [5] [6]

Vinyl alcohol can be stabilized by controlling the water concentration in the system and utilizing the kinetic favorability of the deuterium-produced kinetic isotope effect (kH+/kD+ = 4.75, kH2O/kD2O = 12). Deuterium stabilization can be accomplished through hydrolysis of a ketene precursor in the presence of a slight stoichiometric excess of heavy water (D2O). Studies show that the tautomerization process is significantly inhibited at ambient temperatures ( kt ≈ 10−6 M/s), and the half-life of the enol form can easily be increased to t1/2 = 42 minutes for first-order hydrolysis kinetics. [7]

Relationship to poly(vinyl alcohol)

Because of the instability of vinyl alcohol, the thermoplastic polyvinyl alcohol (PVA or PVOH) is made indirectly by polymerization of vinyl acetate followed by hydrolysis of the ester bonds (Ac = acetyl; HOAc = acetic acid): [8]

n CH2=CHOAc → (CH2−CHOAc)n
(CH2−CHOAc)n + n H2O → (CH2−CHOH)n + n HOAc

As a ligand

Several metal complexes are known that contain vinyl alcohol as a ligand. One example is Pt(acac)(η2-C2H3OH)Cl. [9]

Occurrence in interstellar medium

Vinyl alcohol was detected in the molecular cloud Sagittarius B in 2001, the last of the three stable isomers of C
2
H
4
O
(after acetaldehyde and ethylene oxide) to be detected in space. [10] [11] Its stability in the (dilute) interstellar medium shows that its tautomerization does not happen unimolecularly, [11] a fact attributed to the size of the activation energy barrier to the rearrangement being insurmountable at temperatures present in interstellar space. [12] The vinyl alcohol to acetaldehyde rearrangement is the only keto-enol tautomerisation to have been detected in deep space, induced by the provision of secondary electrons from galactic cosmic rays. [12]

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Ketone</span> Organic compounds of the form >C=O

In organic chemistry, a ketone is an organic compound with the structure R−C(=O)−R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group −C(=O)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and in industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.

<span class="mw-page-title-main">Aldehyde</span> Organic compound containing the functional group R−CH=O

In organic chemistry, an aldehyde is an organic compound containing a functional group with the structure R−CH=O. The functional group itself can be referred to as an aldehyde but can also be classified as a formyl group. Aldehydes are a common motif in many chemicals important in technology and biology.

Acetaldehyde (IUPAC systematic name ethanal) is an organic chemical compound with the formula CH3 CHO, sometimes abbreviated as MeCHO. It is a colorless liquid or gas, boiling near room temperature. It is one of the most important aldehydes, occurring widely in nature and being produced on a large scale in industry. Acetaldehyde occurs naturally in coffee, bread, and ripe fruit, and is produced by plants. It is also produced by the partial oxidation of ethanol by the liver enzyme alcohol dehydrogenase and is a contributing cause of hangover after alcohol consumption. Pathways of exposure include air, water, land, or groundwater, as well as drink and smoke. Consumption of disulfiram inhibits acetaldehyde dehydrogenase, the enzyme responsible for the metabolism of acetaldehyde, thereby causing it to build up in the body.

<span class="mw-page-title-main">Dicarbonyl</span> Molecule containing two adjacent C=O groups

In organic chemistry, a dicarbonyl is a molecule containing two carbonyl groups. Although this term could refer to any organic compound containing two carbonyl groups, it is used more specifically to describe molecules in which both carbonyls are in close enough proximity that their reactivity is changed, such as 1,2-, 1,3-, and 1,4-dicarbonyls. Their properties often differ from those of monocarbonyls, and so they are usually considered functional groups of their own. These compounds can have symmetrical or unsymmetrical substituents on each carbonyl, and may also be functionally symmetrical or unsymmetrical.

<span class="mw-page-title-main">Enamine</span> Class of chemical compounds

An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates.

<span class="mw-page-title-main">Azulene</span> Chemical compound

Azulene is an aromatic organic compound and an isomer of naphthalene. Naphthalene is colourless, whereas azulene is dark blue. The compound is named after its colour, as "azul" is Spanish for blue. Two terpenoids, vetivazulene (4,8-dimethyl-2-isopropylazulene) and guaiazulene (1,4-dimethyl-7-isopropylazulene), that feature the azulene skeleton are found in nature as constituents of pigments in mushrooms, guaiac wood oil, and some marine invertebrates.

<span class="mw-page-title-main">Enol</span> Organic compound with a C=C–OH group

In organic chemistry, alkenols 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 terms enol and alkenol are portmanteaus deriving from "-ene"/"alkene" and the "-ol" suffix indicating the hydroxyl group of alcohols, dropping the terminal "-e" of the first term. Generation of enols often involves deprotonation at the α position to the carbonyl group—i.e., removal of the hydrogen atom there as a proton H+. When this proton is not returned at the end of the stepwise process, the result is an anion termed an enolate. The enolate structures shown are schematic; a more modern representation considers the molecular orbitals that are formed and occupied by electrons in the enolate. Similarly, generation of the enol often is accompanied by "trapping" or masking of the hydroxy group as an ether, such as a silyl enol ether.

<span class="mw-page-title-main">Tautomer</span> Structural isomers of chemical compounds that readily interconvert

Tautomers are structural isomers of chemical compounds that readily interconvert. The chemical reaction interconverting the two is called tautomerization. This conversion commonly results from the relocation of a hydrogen atom within the compound. The phenomenon of tautomerization is called tautomerism, also called desmotropism. Tautomerism is for example relevant to the behavior of amino acids and nucleic acids, two of the fundamental building blocks of life.

<span class="mw-page-title-main">Acetylacetone</span> Chemical compound

Acetylacetone is an organic compound with the chemical formula CH3−C(=O)−CH2−C(=O)−CH3. It is classified as a 1,3-diketone. It exists in equilibrium with a tautomer CH3−C(=O)−CH=C(−OH)−CH3. The mixture is a colorless liquid. These tautomers interconvert so rapidly under most conditions that they are treated as a single compound in most applications. Acetylacetone is a building block for the synthesis of many coordination complexes as well as heterocyclic compounds.

<span class="mw-page-title-main">Wacker process</span> Chemical reaction

The Wacker process or the Hoechst-Wacker process refers to the oxidation of ethylene to acetaldehyde in the presence of palladium(II) chloride and copper(II) chloride as the catalyst. This chemical reaction was one of the first homogeneous catalysis with organopalladium chemistry applied on an industrial scale.

<span class="mw-page-title-main">Vinyl acetate</span> Chemical compound

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

<span class="mw-page-title-main">Phloroglucinol</span> Chemical compound

Phloroglucinol is an organic compound with the formula C6H3(OH)3. It is a colorless solid. It is used in the synthesis of pharmaceuticals and explosives. Phloroglucinol is one of three isomeric benzenetriols. The other two isomers are hydroxyquinol (1,2,4-benzenetriol) and pyrogallol (1,2,3-benzenetriol). Phloroglucinol, and its benzenetriol isomers, are still defined as "phenols" according to the IUPAC official nomenclature rules of chemical compounds. Many such monophenolics are often termed polyphenols.

<span class="mw-page-title-main">Enol ether</span> Class of chemical compounds

In organic chemistry an enol ether is an alkene with an alkoxy substituent. The general structure is R2C=CR-OR where R = H, alkyl or aryl. A common subfamily of enol ethers are vinyl ethers, with the formula ROCH=CH2. Important enol ethers include the reagent 3,4-dihydropyran and the monomers methyl vinyl ether and ethyl vinyl ether.

<span class="mw-page-title-main">Glycolaldehyde</span> Organic compound (HOCH2−CHO)

Glycolaldehyde is the organic compound with the formula HOCH2−CHO. It is the smallest possible molecule that contains both an aldehyde group and a hydroxyl group. It is a highly reactive molecule that occurs both in the biosphere and in the interstellar medium. It is normally supplied as a white solid. Although it conforms to the general formula for carbohydrates, Cn(H2O)n, it is not generally considered to be a saccharide.

In enzymology, phenylpyruvate tautomerase or Macrophage migration inhibitory factor is an enzyme that catalyzes the chemical reaction

<span class="mw-page-title-main">Johann Georg Anton Geuther</span> German chemist (1833–1889)

Johann Georg Anton Geuther was a German chemist. His work in organic and inorganic chemistry influenced the development of coordination chemistry. Geuther spent most of his academic career at the University of Jena where he discovered ethyl acetoacetate, a key compound for chemical synthesis and for the discovery of tautomerism.

Living cationic polymerization is a living polymerization technique involving cationic propagating species. It enables the synthesis of very well defined polymers and of polymers with unusual architecture such as star polymers and block copolymers and living cationic polymerization is therefore as such of commercial and academic interest.

<span class="mw-page-title-main">Vinylsulfonic acid</span> Chemical compound

Vinylsulfonic acid is the organosulfur compound with the chemical formula CH2=CHSO3H. It is the simplest unsaturated sulfonic acid. The C=C double bond is a site of high reactivity. Polymerization gives polyvinylsulfonic acid, especially when used as a comonomer with functionalized vinyl and (meth)acrylic acid compounds. It is a colorless, water-soluble liquid, although commercial samples can appear yellow or even red.

<span class="mw-page-title-main">1,2-Cyclopentanedione</span> Chemical compound

1,2-Cyclopentanedione is the organic compound with the formula (CH2)3(CO)2. It is one of two isomeric cyclopentanediones, the other being 1,3-cyclopentanedione. It was first prepared by base-induced condensation of di ethylglutarate with diethyloxalate, followed by hydrolysis of the resulting diketodiester followed by decarboxylation. The enol is predicted to be about 1-3 kcal/mol more stable than the diketo form. The enol structure has been confirmed by X-ray crystallography.

References

  1. 1 2 Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, p. 101, ISBN   978-0-471-72091-1
  2. Clayden, Jonathan; Greeves, Nick; Warren, Stuart (2012). Organic Chemistry (2nd ed.). Oxford University Press. pp. 456–57. ISBN   978-0-19-927029-3.
  3. R.D. Johnson III. "CCCBDB NIST Standard Reference Database" . Retrieved 2014-08-30.
  4. Keith, J. A.; Henry, P. M. (2009). "The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations". Angew. Chem. Int. Ed. 48 (48): 9038–9049. doi:10.1002/anie.200902194. PMID   19834921.
  5. Heazlewood, B. R.; Maccarone, A. T.; Andrews, D. U.; Osborn, D. L.; Harding, L. B.; Klippenstein, S. J.; Jordan, M. J. T.; Kable, S. H. (2011). "Near-threshold H/D exchange in CD3CHO photodissociation". Nature Chemistry . 3 (6): 443−448. Bibcode:2011NatCh...3..443H. doi:10.1038/nchem.1052. PMID   21602858.
  6. Andrews, D. U.; Heazlewood, B. R.; Maccarone, A. T.; Conroy, T.; Payne, R. J.; Jordan, M. J. T.; Kable, S. H. (2012). "Photo-tautomerization of acetaldehyde to vinyl alcohol: A potential route to tropospheric acids". Science . 337 (6099): 1203–1206. Bibcode:2012Sci...337.1203A. doi:10.1126/science.1220712. PMID   22903524. S2CID   42079807.
  7. Cederstav, Anna K.; Novak, Bruce M. (1994). "Investigations into the Chemistry of Thermodynamically Unstable Species. The Direct Polymerization of Vinyl Alcohol, the Enolic Tautomer of Acetaldehyde". Journal of the American Chemical Society . 100 (9): 4073–4074. doi:10.1021/ja00088a051.
  8. Hallensleben ML (2000). "Polyvinyl Compounds, Others". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a21_743. ISBN   978-3527306732.
  9. Cotton, F. A.; Francis, J. N.; Frenz, B. A.; Tsutsui, M. (1973). "Structure of a dihapto(vinyl alcohol) complex of platinum(II)". Journal of the American Chemical Society . 95 (8): 2483–6. doi:10.1021/ja00789a011.
  10. Blue, Charles (October 1, 2001). "Scientists Toast the Discovery of Vinyl Alcohol in Interstellar Space" (Press release). National Radio Astronomy Observatory . Retrieved December 20, 2006.
  11. 1 2 Turner, B. E.; Apponi, A. J. (2001). "Microwave Detection of Interstellar Vinyl Alcohol, CH
    2
    =CHOH
    "
    . The Astrophysical Journal . 561 (2): L207–L210. doi: 10.1086/324762 .
  12. 1 2 Kleimeier, N. Fabian; Kaiser, Ralf I. (2021). "Interstellar Enolization-Acetaldehyde (CH
    3
    CHO
    ) and Vinyl Alcohol (H
    2
    CCH(OH)
    ) as a Case Study". ChemPhysChem . 22 (12): 1229–1236. doi:10.1002/cphc.202100111. PMID   33913232. S2CID   233447839.