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Malonic acid (
IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
systematic name: propanedioic acid) is a dicarboxylic acid with structure CH2(COOH)2. The ionized form of malonic acid, as well as its
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 and
salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quanti ...
s, are known as malonates. For example, diethyl malonate is malonic acid's
diethyl In organic chemistry, an ethyl group (abbr. Et) is an alkyl substituent with the formula , derived from ethane (). ''Ethyl'' is used in the International Union of Pure and Applied Chemistry's nomenclature of organic chemistry for a saturated t ...
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 ...
. The name originates from the
Greek Greek may refer to: Greece Anything of, from, or related to Greece, a country in Southern Europe: *Greeks, an ethnic group. *Greek language, a branch of the Indo-European language family. **Proto-Greek language, the assumed last common ancestor ...
word μᾶλον (''malon'') meaning 'apple'.


History

Malonic acid is a naturally occurring substance found in many fruits and vegetables. There is a suggestion that
citrus ''Citrus'' is a genus of flowering trees and shrubs in the rue family, Rutaceae. Plants in the genus produce citrus fruits, including important crops such as oranges, lemons, grapefruits, pomelos, and limes. The genus ''Citrus'' is nati ...
fruits produced in
organic farming Organic farming, also known as ecological farming or biological farming,Labelling, article 30 o''Regulation (EU) 2018/848 of the European Parliament and of the Council of 30 May 2018 on organic production and labelling of organic products and re ...
contain higher levels of malonic acid than fruits produced in conventional agriculture. Malonic acid was first prepared in 1858 by the French chemist Victor Dessaignes via the oxidation of malic acid.


Structure and preparation

The structure has been determined by X-ray
crystallography Crystallography is the experimental science of determining the arrangement of atoms in crystalline solids. Crystallography is a fundamental subject in the fields of materials science and solid-state physics (condensed matter physics). The wo ...
and extensive property data including for condensed phase thermochemistry are available from the
National Institute of Standards and Technology The National Institute of Standards and Technology (NIST) is an agency of the United States Department of Commerce whose mission is to promote American innovation and industrial competitiveness. NIST's activities are organized into Outline of p ...
. A classical preparation of malonic acid starts from
chloroacetic acid Chloroacetic acid, industrially known as monochloroacetic acid (MCA), is the organochlorine compound with the formula ClCH2CO2H. This carboxylic acid is a useful building block in organic synthesis. It is a colorless solid. Related compounds a ...
: Sodium carbonate generates the sodium
salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of salts; salt in the form of a natural crystalline mineral is known as rock salt or halite. Salt is present in vast quanti ...
, which is then reacted with
sodium cyanide Sodium cyanide is a poisonous compound with the formula Na C N. It is a white, water-soluble solid. Cyanide has a high affinity for metals, which leads to the high toxicity of this salt. Its main application, in gold mining, also exploits its h ...
to provide the sodium salt of cyanoacetic acid via a
nucleophilic substitution In chemistry, a nucleophilic substitution is a class of chemical reaction A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass c ...
. The nitrile group can be hydrolyzed with
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and alkal ...
to sodium malonate, and acidification affords malonic acid. Industrially, however, malonic acid is produced by hydrolysis of
dimethyl malonate Dimethyl malonate is a diester derivative of malonic acid. It is a common reagent for organic synthesis used, for example, as a precursor for barbituric acid. It is also used in the malonic ester synthesis. It can be synthesized from dimethoxymeth ...
or diethyl malonate. It has also been produced through fermentation of glucose.


Organic reactions

Malonic acid reacts as a typical carboxylic acid: forming
amide In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula , where R, R', and R″ represent organic groups or hydrogen atoms. The amide group is called a peptide bond when it is ...
, ester, anhydride, and
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride s ...
derivatives. Malonic anhydride can be used as an intermediate to mono-ester or amide derivatives, while
malonyl chloride Malonyl chloride is the organic compound with the formula CH2(COCl)2. It is the acyl chloride derivative of malonic acid. It is a colorless liquid although samples are often deeply colored owing to impurities. The compound degrades at room temper ...
is most useful to obtain diesters or diamides. In a well-known reaction, malonic acid condenses with
urea Urea, also known as carbamide, is an organic compound with chemical formula . This amide has two amino groups (–) joined by a carbonyl functional group (–C(=O)–). It is thus the simplest amide of carbamic acid. Urea serves an important ...
to form barbituric acid. Malonic acid may also be condensed with
acetone Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour. Acetone is miscible wi ...
to form
Meldrum's acid Meldrum's acid or 2,2-dimethyl-1,3-dioxane-4,6-dione is an organic compound with formula . Its molecule has a heterocyclic core with four carbon and two oxygen atoms; the formula can also be written as . It is a crystalline colorless solid, spar ...
, a versatile intermediate in further transformations. The esters of malonic acid are also used as a CH2COOH synthon in the malonic ester synthesis. Additionally, the
coenzyme A Coenzyme A (CoA, SHCoA, CoASH) is a coenzyme, notable for its role in the synthesis and oxidation of fatty acids, and the oxidation of pyruvate in the citric acid cycle. All genomes sequenced to date encode enzymes that use coenzyme A as a subs ...
derivative of malonate,
malonyl-CoA Malonyl-CoA is a coenzyme A derivative of malonic acid. Functions It plays a key role in chain elongation in fatty acid biosynthesis and polyketide biosynthesis. Fatty acid biosynthesis Malonyl-CoA provides 2-carbon units to fatty acids and com ...
, is an important precursor in fatty acid biosynthesis along with acetyl CoA. Malonyl CoA is formed from acetyl CoA by the action of
acetyl-CoA carboxylase Acetyl-CoA carboxylase (ACC) is a biotin-dependent enzyme () that catalyzes the irreversible carboxylation of acetyl-CoA to produce malonyl-CoA through its two catalytic activities, biotin carboxylase (BC) and carboxyltransferase (CT). ACC ...
, and the malonate is transferred to an acyl carrier protein to be added to a fatty acid chain.


Briggs–Rauscher reaction

Malonic acid is a key component in the Briggs–Rauscher reaction, the classic example of an oscillating chemical reaction.


Knoevenagel condensation

In Knoevenagel condensation, malonic acid or its diesters are reacted with the
carbonyl In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups. A compound containin ...
group of an
aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl group ...
or
ketone In organic chemistry, a ketone is a functional group 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)– (which contains a carbon-oxygen double bon ...
, followed by a dehydration reaction. When malonic acid itself is used, it is normally because the desired product is one in which a second step has occurred, with loss of
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
, in the so-called Doebner modification. Thus, for example, the reaction product of
acrolein Acrolein (systematic name: propenal) is the simplest unsaturated aldehyde. It is a colorless liquid with a piercing, acrid smell. The smell of burnt fat (as when cooking oil is heated to its smoke point) is caused by glycerol in the burning fa ...
and malonic acid in
pyridine Pyridine is a basic (chemistry), basic heterocyclic compound, heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakl ...
is ''trans-2,4-Pentadienoic acid'' with one carboxylic acid group and not two.


Preparation of carbon suboxide

Carbon suboxide Carbon suboxide, or tricarbon dioxide, is an organic, oxygen-containing chemical compound with formula and structure . Its four cumulative double bonds make it a cumulene. It is one of the stable members of the series of linear oxocarbons , ...
is prepared by warming a dry mixture of phosphorus pentoxide () and malonic acid. It reacts in a similar way to malonic anhydride, forming malonates.


Applications

Malonic acid is a precursor to specialty polyesters. It can be converted into 1,3-propanediol for use in polyesters and polymers (whose usefulness is unclear though). It can also be a component in alkyd resins, which are used in a number of coatings applications for protecting against damage caused by UV light, oxidation, and corrosion. One application of malonic acid is in the coatings industry as a crosslinker for low-temperature cure powder coatings, which are becoming increasingly valuable for heat sensitive substrates and a desire to speed up the coatings process. The global coatings market for automobiles was estimated to be $18.59 billion in 2014 with projected combined annual growth rate of 5.1% through 2022. It is used in a number of manufacturing processes as a high value specialty chemical including the
electronics The field of electronics is a branch of physics and electrical engineering that deals with the emission, behaviour and effects of electrons using electronic devices. Electronics uses active devices to control electron flow by amplification ...
industry, flavors and fragrances industry, specialty solvents, polymer crosslinking, and pharmaceutical industry. In 2004, annual global production of malonic acid and related diesters was over 20,000 metric tons. Potential growth of these markets could result from advances in industrial biotechnology that seeks to displace petroleum-based chemicals in industrial applications. In 2004, malonic acid was listed by the US Department of Energy as one of the top 30 chemicals to be produced from biomass. In food and drug applications, malonic acid can be used to control acidity, either as an excipient in pharmaceutical formulation or natural preservative additive for foods. Malonic acid is used as a building block chemical to produce numerous valuable compounds, including the flavor and fragrance compounds gamma-nonalactone,
cinnamic acid 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 n ...
, and the pharmaceutical compound valproate. Malonic acid (up to 37.5% w/w) has been used to cross-link corn and potato starches to produce a biodegradable thermoplastic; the process is performed in water using non-toxic catalysts. Starch-based polymers comprised 38% of the global biodegradable polymers market in 2014 with food packaging, foam packaging, and compost bags as the largest end-use segments.
Eastman Eastman may refer to: People * Eastman (surname) * Eastman Nixon Jacobs (1902–1987), American aerodynamicist * John Eastman (b 1960), American lawyer and founding director of the Center for Constitutional Jurisprudence * Jonathan Eastman Johnso ...
Kodak company and others use malonic acid and derivatives as a surgical adhesive.


Pathology

If elevated malonic acid levels are accompanied by elevated
methylmalonic acid Methylmalonic acid (MMA) (conjugate base methylmalonate) is a dicarboxylic acid that is a ''C''- methylated derivative of malonate. The coenzyme A linked form of methylmalonic acid, methylmalonyl-CoA, is converted into succinyl-CoA by methylma ...
levels, this may indicate the metabolic disease combined malonic and methylmalonic aciduria (CMAMMA). By calculating the malonic acid to methylmalonic acid ratio in blood plasma, CMAMMA can be distinguished from classic methylmalonic acidemia.


Biochemistry

Malonic acid is the classic example of a competitive inhibitor of the
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different molecule ...
succinate dehydrogenase (complex II), in the respiratory electron transport chain. It binds to the active site of the enzyme without reacting, competing with the usual substrate succinate but lacking the −CH2CH2− group required for dehydrogenation. This observation was used to deduce the structure of the active site in succinate dehydrogenase. Inhibition of this enzyme decreases cellular respiration. Since malonic acid is a natural component of many foods, it is present in mammals including humans.


Related Chemicals

The fluorinated version of malonic acide is difluoromalonic acidbr>
Malonic acid is Acid#Polyprotic_acids, diprotic; that is, it can donate two
protons A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron m ...
per molecule. Its first pK_a is 2.8 and the second is 5.7. Thus the malonate ion can be or . Malonate or propanedioate compounds include
salts In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively ...
and
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 of malonic acid, such as * Diethyl malonate *
Dimethyl malonate Dimethyl malonate is a diester derivative of malonic acid. It is a common reagent for organic synthesis used, for example, as a precursor for barbituric acid. It is also used in the malonic ester synthesis. It can be synthesized from dimethoxymeth ...
* Disodium malonate *
Malonyl-CoA Malonyl-CoA is a coenzyme A derivative of malonic acid. Functions It plays a key role in chain elongation in fatty acid biosynthesis and polyketide biosynthesis. Fatty acid biosynthesis Malonyl-CoA provides 2-carbon units to fatty acids and com ...


References


External links


Calculator: Water and solute activities in aqueous malonic acid
{{Authority control Dicarboxylic acids