Maleic acid or ''cis''-butenedioic acid is an
organic compound
In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. Th ...
that is a
dicarboxylic acid, a molecule with two
carboxyl groups. Its chemical formula is HO
2CCH=CHCO
2H. Maleic acid is the
''cis''-isomer of butenedioic acid, whereas
fumaric acid is the ''trans''-isomer. It is mainly used as a precursor to fumaric acid, and relative to its parent
maleic anhydride, maleic acid has few applications.
Physical properties
Maleic acid has a ''
heat of combustion
The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it.
The ''calorific value'' is the total energy rele ...
'' of -1,355 kJ/mol., 22.7 kJ/mol higher than that of fumaric acid. Maleic acid is more soluble in water than
fumaric acid. The melting point of maleic acid (135 °C) is also much lower than that of fumaric acid (287 °C). Both properties of maleic acid can be explained on account of the
intramolecular hydrogen bond
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a l ...
ing that takes place in maleic acid at the expense of intermolecular interactions, and that are not possible in
fumaric acid for geometric reasons.
Production and industrial applications
In industry, maleic acid is derived 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
maleic anhydride, the latter being produced by
oxidation
Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
of
benzene
Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms ...
or
butane
Butane () or ''n''-butane is an alkane with the formula C4H10. Butane is a gas at room temperature and atmospheric pressure. Butane is a highly flammable, colorless, easily liquefied gas that quickly vaporizes at room temperature. The name but ...
.
Maleic acid is an industrial raw material for the production of
glyoxylic acid by
ozonolysis.
Maleic acid may be used to form acid addition salts with drugs to make them more stable, such as indacaterol maleate.
Maleic acid is also used as an adhesion promoter for different substrates, such as nylon and zinc coated metals e.g galvanized steel, in methyl methacrylate based adhesives.
Isomerization to fumaric acid
The major industrial use of maleic acid is its conversion to
fumaric acid. This conversion, an
isomerization, is
catalysed by a variety of reagents, such as
mineral acids and
thiourea. Again, the large difference in water solubility makes fumaric acid purification easy.
The
isomerization is a popular topic in schools. Maleic acid and fumaric acid do not spontaneously interconvert because rotation around a carbon carbon
double bond is not energetically favourable. However, conversion of the ''cis'' isomer into the ''trans'' isomer is possible by
photolysis
Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule. ...
in the presence of a small amount of
bromine
Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...
. Light converts elemental bromine into a bromine
radical, which attacks the alkene in a
radical addition reaction to a bromo-alkane radical; and now single bond rotation is possible. The bromine radicals recombine and fumaric acid is formed. In another method (used as a classroom demonstration), maleic acid is transformed into
fumaric acid through the process of heating the maleic acid in
hydrochloric acid
Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the dige ...
solution. Reversible addition (of H
+) leads to free rotation about the central C-C bond and formation of the more stable and less soluble fumaric acid.
Some bacteria produce the enzyme
maleate isomerase, which is used by bacteria in
nicotinate metabolism. This enzyme catalyses isomerization between fumarate and maleate.
Other reactions
Although not practised commercially, maleic acid can be converted into
maleic anhydride by
dehydration
In physiology, dehydration is a lack of total body water, with an accompanying disruption of metabolic processes. It occurs when free water loss exceeds free water intake, usually due to exercise, disease, or high environmental temperature. Mil ...
, to
malic acid by
hydration Hydration may refer to:
* Hydrate, a substance that contains water
* Hydration enthalpy, energy released through hydrating a substance
* Hydration reaction, a chemical addition reaction where a hydroxyl group and proton are added to a compound
* ...
, and to
succinic acid by
hydrogenation
Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic ...
(
ethanol
Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
/
palladium on carbon
Palladium on carbon, often referred to as Pd/C, is a form of palladium used as a catalyst. The metal is supported on activated carbon to maximize its surface area and activity.
Uses Hydrogenation
Palladium on carbon is used for catalytic hydrog ...
).
It reacts with
thionyl chloride or
phosphorus pentachloride
Phosphorus pentachloride is the chemical compound with the formula PCl5. It is one of the most important phosphorus chlorides, others being PCl3 and POCl3. PCl5 finds use as a chlorinating reagent. It is a colourless, water-sensitive and mois ...
to give the maleic acid chloride (it is not possible to isolate the mono acid chloride). Maleic acid, being electrophilic, participates as a
dienophile in many
Diels-Alder reactions.
Maleates
The maleate ion is the ionized form of maleic acid. The maleate ion is useful in
biochemistry
Biochemistry or biological chemistry is the study of chemical processes within and relating to living organisms. A sub-discipline of both chemistry and biology, biochemistry may be divided into three fields: structural biology, enzymology and ...
as an inhibitor of
transaminase reactions. Maleic acid
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 ...
s are also called maleates, for instance
dimethyl maleate
Dimethyl maleate is an organic compound with the formula C6H8O4. It is the dimethyl ester of maleic acid.
Synthesis
Dimethyl maleate can be synthesized from maleic anhydride and methanol, with sulfuric acid acting as acid catalyst, via a nu ...
.
Use in pharmaceutical drugs
Many drugs that contain
amine
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent ...
s are provided as the maleate
acid salt, e.g.
carfenazine,
chlorpheniramine
Chlorphenamine (CP, CPM), also known as chlorpheniramine, is an antihistamine used to treat the symptoms of allergic conditions such as allergic rhinitis (hay fever). It is taken by mouth. The medication takes effect within two hours and lasts ...
,
pyrilamine
Mepyramine, also known as pyrilamine, is a first generation antihistamine, targeting the H1 receptor as an inverse agonist. Mepyramine rapidly permeates the brain, often causing drowsiness. It is often sold as a maleate salt, pyrilamine maleate. ...
,
methylergonovine
Methylergometrine, also known as methylergonovine and sold under the brand name Methergine, is a medication of the ergoline and lysergamide groups which is used as an oxytocic in obstetrics and in the treatment of migraine. It reportedly produce ...
, and
thiethylperazine
Thiethylperazine (Torecan, Norzine) is an antiemetic of the phenothiazine class. It is an antagonist of dopamine receptors (DRD1, DRD2, DRD4) as well as of 5-HT2A, 5-HT2C receptors, mAChRs (1 through 5), α1 adrenergic receptor and H1 recepto ...
.
See also
*
Fumaric acid
*
Malic acid
*
Malonic acid
*
Succinic acid
References
External links
International Chemical Safety Card 1186Calculator: Water and solute activities in aqueous maleic acid
{{Authority control
Dicarboxylic acids
Enoic acids