Maleic acid

Last updated
Maleic acid
Maleinsaure.svg
Maleic-acid-3D-balls-A.png
Maleic-acid-3D-vdW-A.png
Sample of maleic acid.jpg
Names
Preferred IUPAC name
(2Z)-But-2-enedioic acid
Other names
(Z)-Butenedioic acid; cis-Butenedioic acid; Malenic acid; Maleinic acid; Toxilic acid
Identifiers
3D model (JSmol)
3DMet
605762
ChEBI
ChEMBL
ChemSpider
DrugBank
ECHA InfoCard 100.003.403 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-742-5
49854
KEGG
PubChem CID
RTECS number
  • OM9625000
UNII
  • InChI=1S/C4H4O4/c5-3(6)1-2-4(7)8/h1-2H,(H,5,6)(H,7,8)/b2-1- Yes check.svgY
    Key: VZCYOOQTPOCHFL-UPHRSURJSA-N Yes check.svgY
  • InChI=1/C4H4O4/c5-3(6)1-2-4(7)8/h1-2H,(H,5,6)(H,7,8)/b2-1-
    Key: VZCYOOQTPOCHFL-UPHRSURJBG
  • O=C(O)\C=C/C(=O)O
Properties
C4H4O4
Molar mass 116.072 g·mol−1
AppearanceWhite solid
Density 1.59 g/cm3 [1]
Melting point 135 °C (275 °F; 408 K) (decomposes) [2]
478.8 g/L at 20 C [2]
Acidity (pKa)pka1 = 1.90
pka2 = 6.07 [3]
-49.71·10−6 cm3/mol
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H302, H315, H317, H319, H335
P261, P264, P270, P271, P272, P280, P301+P312, P302+P352, P304+P340, P305+P351+P338, P312, P321, P330, P332+P313, P333+P313, P337+P313, P362, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Safety data sheet (SDS) MSDS from J. T. Baker
Related compounds
fumaric acid
succinic acid
crotonic acid
Related compounds
maleic anhydride
maleimide
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 ?)

Maleic acid or cis-butenedioic acid is an organic compound that is a dicarboxylic acid, a molecule with two carboxyl groups. Its chemical formula is HO2CCH=CHCO2H. 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, which has many applications.. [4]

Contents

Physical properties

Maleic acid has a heat of combustion of -1,355 kJ/mol., [5] 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). As confirmed by X-ray crystallography, maleic acid is planar. Two normal hydrogen bonds are observed, one intramolecular and one intermolecular. Crystallographic analysis shows that the intramolecular hydrogen bond is little affected in the monopotassium salt. [6]

Production and industrial applications

In industry, maleic acid is derived by hydrolysis of maleic anhydride, the latter being produced by oxidation of benzene or butane. [4]

Maleic acid is an industrial raw material for the production of glyoxylic acid by ozonolysis. [7]

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 in the presence of a small amount of bromine. [8] 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 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, to malic acid by hydration, and to succinic acid by hydrogenation (ethanol / palladium on carbon). [9] It reacts with thionyl chloride or phosphorus pentachloride 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 as an inhibitor of transaminase reactions. Maleic acid esters are also called maleates, for instance dimethyl maleate.

Use in pharmaceutical drugs

Many drugs that contain amines are provided as the maleate acid salt, e.g. carfenazine, chlorpheniramine, pyrilamine, methylergonovine, and thiethylperazine. [10]

See also

Related Research Articles

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

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

A halogen addition reaction is a simple organic reaction where a halogen molecule is added to the carbon–carbon double bond of an alkene functional group.

In biochemistry, isomerases are a general class of enzymes that convert a molecule from one isomer to another. Isomerases facilitate intramolecular rearrangements in which bonds are broken and formed. The general form of such a reaction is as follows:

<span class="mw-page-title-main">Fumaric acid</span> Organic compound

Fumaric acid is an organic compound with the formula HO2CCH=CHCO2H. A white solid, fumaric acid occurs widely in nature. It has a fruit-like taste and has been used as a food additive. Its E number is E297. The salts and esters are known as fumarates. Fumarate can also refer to the C
4
H
2
O2−
4
ion (in solution). Fumaric acid is the trans isomer of butenedioic acid, while maleic acid is the cis isomer.

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

Cinnamic acid is an organic compound with the formula C6H5-CH=CH-COOH. It is a white crystalline compound that is slightly soluble in water, and freely soluble in many organic solvents. Classified as an unsaturated carboxylic acid, it occurs naturally in a number of plants. It exists as both a cis and a trans isomer, although the latter is more common.

In organic chemistry, hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the production of aldehydes from alkenes. This chemical reaction entails the net addition of a formyl group and a hydrogen atom to a carbon-carbon double bond. This process has undergone continuous growth since its invention: production capacity reached 6.6×106 tons in 1995. It is important because aldehydes are easily converted into many secondary products. For example, the resultant aldehydes are hydrogenated to alcohols that are converted to detergents. Hydroformylation is also used in speciality chemicals, relevant to the organic synthesis of fragrances and pharmaceuticals. The development of hydroformylation is one of the premier achievements of 20th-century industrial chemistry.

In organic chemistry, an electrocyclic reaction is a type of pericyclic rearrangement where the net result is one pi bond being converted into one sigma bond or vice versa. These reactions are usually categorized by the following criteria:

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

Bromic acid, also known as hydrogen bromate, is an oxoacid with the molecular formula HBrO3. It only exists in aqueous solution. It is a colorless solution that turns yellow at room temperature as it decomposes to bromine. Bromic acid and bromates are powerful oxidizing agents and are common ingredients in Belousov–Zhabotinsky reactions. Belousov-Zhabotinsky reactions are a classic example of non-equilibrium thermodynamics.

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

Crotonic acid ((2E)-but-2-enoic acid) is a short-chain unsaturated carboxylic acid described by the formula CH3CH=CHCO2H. The name crotonic acid was given because it was erroneously thought to be a saponification product of croton oil. It crystallizes as colorless needles from hot water. With a cis-alkene, Isocrotonic acid is an isomer of crotonic acid. Crotonic acid is soluble in water and many organic solvents. Its odor is similar to that of butyric acid.

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

Cycloheptene is a 7-membered cycloalkene with a flash point of −6.7 °C. It is a raw material in organic chemistry and a monomer in polymer synthesis. Cycloheptene can exist as either the cis- or the trans-isomer.

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

Succinic anhydride, is an organic compound with the molecular formula (CH2CO)2O. This colorless solid is the acid anhydride of succinic acid.

Polyester resins are synthetic resins formed by the reaction of dibasic organic acids and polyhydric alcohols. Maleic anhydride is a commonly used raw material with diacid functionality in unsaturated polyester resins. Unsaturated polyester resins are used in sheet moulding compound, bulk moulding compound and the toner of laser printers. Wall panels fabricated from polyester resins reinforced with fiberglass—so-called fiberglass reinforced plastic (FRP)—are typically used in restaurants, kitchens, restrooms and other areas that require washable low-maintenance walls. They are also used extensively in cured-in-place pipe applications. Departments of Transportation in the USA also specify them for use as overlays on roads and bridges. In this application they are known AS Polyester Concrete Overlays (PCO). These are usually based on isophthalic acid and cut with styrene at high levels—usually up to 50%. Polyesters are also used in anchor bolt adhesives though epoxy based materials are also used. Many companies have and continue to introduce styrene free systems mainly due to odor issues, but also over concerns that styrene is a potential carcinogen. Drinking water applications also prefer styrene free. Most polyester resins are viscous, pale coloured liquids consisting of a solution of a polyester in a reactive diluent which is usually styrene, but can also include vinyl toluene and various acrylates.

The Barton reaction, also known as the Barton nitrite ester reaction, is a photochemical reaction that involves the photolysis of an alkyl nitrite to form a δ-nitroso alcohol.

<span class="mw-page-title-main">Maleate isomerase</span>

In enzymology, a maleate isomerase, or maleate cis-tran isomerase, is a member of the Asp/Glu racemase superfamily discovered in bacteria. It is responsible for catalyzing cis-trans isomerization of the C2-C3 double bond in maleate to produce fumarate, which is a critical intermediate in citric acid cycle. The presence of an exogenous mercaptan is required for catalysis to happen.

<span class="mw-page-title-main">Isomer</span> Chemical compounds with the same molecular formula but different atomic arrangements

In chemistry, isomers are molecules or polyatomic ions with identical molecular formula – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism refers to the existence or possibility of isomers.

<span class="mw-page-title-main">Organorhodium chemistry</span> Field of study

Organorhodium chemistry is the chemistry of organometallic compounds containing a rhodium-carbon chemical bond, and the study of rhodium and rhodium compounds as catalysts in organic reactions.

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

Citraconic acid is an organic compound with the formula CH3C2H(CO2H)2. It is a white solid. The alkene is cis. The related trans alkene is called mesaconic acid. It is one of the pyrocitric acids formed upon the heating of citric acid. Citraconic acid can be produced, albeit inefficiently, by oxidation of xylene and methylbutanols. The acid displays the unusual property of spontaneously forming the anhydride, which, unlike maleic anhydride, is a liquid at room temperature.

5-Hydroxy-2(5<i>H</i>)-furanone Chemical compound

5-Hydroxy-2(5H)-furanone is a furanone derived from oxidation of furfural using singlet oxygen. This oxidation is carried out generally in methanol or ethanol with a sensitizer like methylene blue or Rose bengal. The mechanism of this reaction is depicted as below.

In organometallic chemistry, a transition metal alkene complex is a coordination compound containing one or more alkene ligands. The inventory is large. Such compounds are intermediates in many catalytic reactions that convert alkenes to other organic products.

α,β-Unsaturated carbonyl compound Functional group of organic compounds

α,β-Unsaturated carbonyl compounds are organic compounds with the general structure (O=CR)−Cα=Cβ-R. Such compounds include enones and enals, but also carboxylic acids and the corresponding esters and amides. In these compounds the carbonyl group is conjugated with an alkene. Unlike the case for carbonyls without a flanking alkene group, α,β-unsaturated carbonyl compounds are susceptible to attack by nucleophiles at the β-carbon. This pattern of reactivity is called vinylogous. Examples of unsaturated carbonyls are acrolein (propenal), mesityl oxide, acrylic acid, and maleic acid. Unsaturated carbonyls can be prepared in the laboratory in an aldol reaction and in the Perkin reaction.

References

  1. Budavari, Susan, ed. (1996), The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.), Merck, ISBN   0911910123
  2. 1 2 Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  3. CRC Handbook of Chemistry and Physics, 73rd ed.; CRC Press: Boca Raton, Florida., 1993
  4. 1 2 Lohbeck, Kurt; Haferkorn, Herbert; Fuhrmann, Werner; Fedtke, Norbert (2000). "Maleic and Fumaric Acids". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a16_053. ISBN   9783527303854.
  5. Maleic Anhydride, Maleic Acid, and Fumaric Acid Archived 2013-11-02 at the Wayback Machine , Huntsman Petrochemical Corporation
  6. M. N. G James, G. J. B Williams (1974). "A Refinement of the Crystal Structure of Maleic Acid". Acta Crystallographica. B30 (5) (5): 1249–1275. Bibcode:1974AcCrB..30.1249J. doi: 10.1107/S0567740874004626 .
  7. DSM glyoxylic acid production Archived 2005-11-30 at the Wayback Machine
  8. Light isomerization experiment Archived 2005-11-27 at the Wayback Machine (from the University of Regensburg, with video)
  9. Kwesi Amoa (2007). "Catalytic Hydrogenation of Maleic Acid at Moderate Pressures A Laboratory Demonstration". Journal of Chemical Education . 84 (12): 1948. Bibcode:2007JChEd..84.1948A. doi:10.1021/ed084p1948.
  10. "NCATS Inxight Drugs — Fumaric acid". drugs.ncats.io. Retrieved 2023-11-10.