Vinyl alcohol, also called ethenol (IUPAC name; not ethanol), is the simplest

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 (). T ...

. With the

formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...

, it is a labile compound that converts to

acetaldehyde Acetaldehyde (IUPAC systematic name ethanal) is an organic chemical compound with the formula CH3 CHO, sometimes abbreviated by chemists as MeCHO (Me = methyl). It is a colorless liquid or gas, boiling near room temperature. It is one of the ...

. It is not a precursor to

polyvinyl alcohol Poly(vinyl alcohol) (PVOH, PVA, or PVAl) is a water- soluble synthetic polymer. It has the idealized formula H2CH(OH)sub>''n''. It is used in papermaking, textile warp sizing, as a thickener and emulsion stabilizer in polyvinyl acetate (PVAc) ...

Synthesis

Vinyl alcohol can be formed by the pyrolytic elimination of water from

ethylene glycol Ethylene glycol ( IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an o ...

at a temperature of 900 °C and low pressure.

Tautomerization of vinyl alcohol to acetaldehyde

Under normal conditions, vinyl alcohol converts (

tautomer Tautomers () are structural isomers (constitutional 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 hy ...

izes) to

: :

At room temperature, acetaldehyde () is more stable than vinyl alcohol () by 42.7 kJ/mol: : Δ''H''_298,g = −42.7 kJ/mol WackerCycleKeith&HenryImp

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. Vinyl alcohol can be stabilized by controlling the water concentration in the system and utilizing the kinetic favorability of the

deuterium Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two stable isotopes of hydrogen (the other being protium, or hydrogen-1). The nucleus of a deuterium atom, called a deuteron, contains one proton and one ...

-produced

kinetic isotope effect In physical organic chemistry, a kinetic isotope effect (KIE) is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. Formally, it is the ratio of rate constants for ...

(''k''_H⁺/''k''_D⁺ = 4.75, ''k''_H₂O/''k''_D₂O = 12). Deuterium stabilization can be accomplished through hydrolysis of a

ketene In organic chemistry, a ketene is an organic compound 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 ethen ...

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 ( ''k''_t ≈ 10⁻⁶ M/s), and the

half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ...

of the enol form can easily be increased to ''t''_1/2 = 42 minutes for first-order hydrolysis kinetics.

Relationship to poly(vinyl alcohol)

Because of the instability of vinyl alcohol, the

thermoplastic A thermoplastic, or thermosoft plastic, is any plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling. Most thermoplastics have a high molecular weight. The polymer chains associate ...

(PVA or PVOH) is made indirectly by polymerization of

vinyl acetate Vinyl acetate is an organic compound with the formula CH3CO2CH=CH2. This colorless liquid is the precursor to polyvinyl acetate and ethene-vinyl acetate copolymers, important industrial polymers. Production The worldwide production capacity of v ...

followed by

hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile. Biological hydrolysi ...

of the

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 ...

bonds (Ac = acetyl; HOAc = acetic acid): : :

As a ligand

Several

metal complexes A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...

are known that contain vinyl alcohol as a

ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...

. One example is Pt(acac)(η²-C₂H₃OH)Cl.

Occurrence in interstellar medium

Vinyl alcohol was detected in the

molecular cloud A molecular cloud, sometimes called a stellar nursery (if star formation is occurring within), is a type of interstellar cloud, the density and size of which permit absorption nebulae, the formation of molecules (most commonly molecular hydroge ...

Sagittarius B. Its stability in the (dilute)

interstellar medium In astronomy, the interstellar medium is the matter and radiation that exist in the space between the star systems in a galaxy. This matter includes gas in ionic, atomic, and molecular form, as well as dust and cosmic rays. It fills interstella ...

shows that its tautomerization does not happen unimolecularly.

References

{{Alcohols Enols Vinyl compounds Organic compounds with 2 carbon atoms