In organic chemistry, a dicarboxylic acid is an organic compound containing two carboxyl groups (). The general molecular formula for dicarboxylic acids can be written as , where R can be aliphatic or aromatic. In general, dicarboxylic acids show similar chemical behavior and reactivity to monocarboxylic acids. Dicarboxylic acids are used in the preparation of copolymers such as polyamides and

polyester Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include natural ...

s. The most widely used dicarboxylic acid in the industry is adipic acid, which is a precursor in the production of nylon. Other examples of dicarboxylic acids include

aspartic acid Aspartic acid (symbol Asp or D; the ionic form is known as aspartate), is an α-amino acid that is used in the biosynthesis of proteins. Like all other amino acids, it contains an amino group and a carboxylic acid. Its α-amino group is in the pro ...

and

glutamic acid Glutamic acid (symbol Glu or E; the ionic form is known as glutamate) is an α-amino acid that is used by almost all living beings in the biosynthesis of proteins. It is a non-essential nutrient for humans, meaning that the human body can synt ...

, two

amino acids Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although hundreds of amino acids exist in nature, by far the most important are the alpha-amino acids, which comprise proteins. Only 22 alpha am ...

in the human body. The name can be abbreviated to diacid.

Linear saturated dicarboxylic acids

The general formula is .Boy Cornils, Peter Lappe "Dicarboxylic Acids, Aliphatic" in Ullmann's Encyclopedia of Industrial Chemistry 2014, Wiley-VCH, Weinheim. The PubChem links gives access to more information on the compounds, including other names, ids, toxicity and safety. Acids from the two-carbon oxalic acid to the ten-member sebacic acid may be remembered using the mnemonic 'Oh My Son, Go And Pray Softly And Silently', and also 'Oh my! Such great Apple Pie, sweet as sugar!'. :

Occurrence

* Adipic acid, despite its name (in Latin, adipis means fat), is not a normal constituent of natural lipids but is a product of oxidative rancidity. It was first obtained by oxidation of castor oil ( ricinoleic acid) with nitric acid. It is now produced industrially by oxidation of cyclohexanol or

cyclohexane Cyclohexane is a cycloalkane with the molecular formula . Cyclohexane is non-polar. Cyclohexane is a colorless, flammable liquid with a distinctive detergent-like odor, reminiscent of cleaning products (in which it is sometimes used). Cyclohexan ...

, mainly for the production of Nylon 6-6. It has several other industrial uses in the production of

adhesive Adhesive, also known as glue, cement, mucilage, or paste, is any non-metallic substance applied to one or both surfaces of two separate items that binds them together and resists their separation. The use of adhesives offers certain advant ...

s, plasticizers, gelatinizing agents,

hydraulic fluid A hydraulic fluid or hydraulic liquid is the medium by which power is transferred in hydraulic machinery. Common hydraulic fluids are based on mineral oil or water. Examples of equipment that might use hydraulic fluids are excavators and backhoe ...

lubricant A lubricant (sometimes shortened to lube) is a substance that helps to reduce friction between surfaces in mutual contact, which ultimately reduces the heat generated when the surfaces move. It may also have the function of transmitting forces, t ...

s, emollients, polyurethane foams, leather tanning, urethane and also as an acidulant in foods. * Pimelic acid (Greek , fat) was also first isolated from oxidized oil. Derivatives of pimelic acid are involved in the biosynthesis of

lysine Lysine (symbol Lys or K) is an α-amino acid that is a precursor to many proteins. It contains an α-amino group (which is in the protonated form under biological conditions), an α-carboxylic acid group (which is in the deprotonated −C ...

. * Suberic acid was first produced by nitric acid oxidation of cork (Latin suber). This acid is also produced when castor oil is oxidised. Suberic acid is used in the manufacture of alkyd resins and in the synthesis of polyamides ( nylon variants). * Azelaic acid's name stems from the action of nitric acid (azote, nitrogen, or azotic, nitric) oxidation of oleic acid or elaidic acid. It was detected among products of rancid fats. Its origin explains for its presence in poorly preserved samples of

linseed oil Linseed oil, also known as flaxseed oil or flax oil (in its edible form), is a colourless to yellowish oil obtained from the dried, ripened seeds of the flax plant (''Linum usitatissimum''). The oil is obtained by pressing, sometimes followed by ...

and in specimens of ointment removed from Egyptian tombs 5000 years old. Azelaic acid was prepared by oxidation of oleic acid with potassium permanganate, but now by oxidative cleavage of oleic acid with chromic acid or by ozonolysis. Azelaic acid is used, as simple esters or branched-chain esters) in the manufacture of plasticizers (for vinyl chloride resins, rubber), lubricants and greases. Azelaic acid is now used in cosmetics (treatment of acne). It displays bacteriostatic and

bactericidal A bactericide or bacteriocide, sometimes abbreviated Bcidal, is a substance which kills bacteria. Bactericides are disinfectants, antiseptics, or antibiotics. However, material surfaces can also have bactericidal properties based solely on their ...

properties against a variety of aerobic and anaerobic micro-organisms present on acne-bearing skin. . Azelaic acid was identified as a molecule that accumulated at elevated levels in some parts of plants and was shown to be able to enhance the resistance of plants to infections. * Sebacic acid, named from sebum ( tallow). Thenard isolated this compound from distillation products of beef tallow in 1802. It is produced industrially by alkali fission of castor oil. Sebacic acid and its derivatives have a variety of industrial uses as plasticizers, lubricants, diffusion pump oils, cosmetics, candles, etc. It is also used in the synthesis of polyamide, as nylon, and of alkyd resins. An isomer, isosebacic acid, has several applications in the manufacture of vinyl resin plasticizers, extrusion plastics, adhesives, ester lubricants, polyesters, polyurethane resins and

synthetic rubber A synthetic rubber is an artificial elastomer. They are polymers synthesized from petroleum byproducts. About 32-million metric tons of rubbers are produced annually in the United States, and of that amount two thirds are synthetic. Synthetic rubbe ...

. * Brassylic acid can be produced from erucic acid by ozonolysis, but also by microorganisms ( ''Candida'' sp.) from

tridecane Tridecane or ''n''-tridecane is an alkane with the chemical formula CH3(CH2)11CH3. Tridecane is a combustible colourless liquid. In industry, they have no specific value aside from being components of various fuels and solvents. In the research ...

. This diacid is produced on a small commercial scale in Japan for the manufacture of fragrances. * Dodecanedioic acid is used in the production of nylon (nylon-6,12), polyamides, coatings, adhesives, greases, polyesters, dyestuffs, detergents, flame retardants, and fragrances. It is now produced by fermentation of long-chain alkanes with a specific strain of ''

Candida tropicalis ''Candida tropicalis'' is a species of yeast in the genus '' Candida''. It is a common pathogen in neutropenic hosts, in whom it may spread through the bloodstream to peripheral organs. For invasive disease, treatments include amphotericin B, ec ...

''. Traumatic acid is its monounsaturated counterpart. * Thapsic acid was isolated from the dried roots of the Mediterranean "deadly carrot", '' Thapsia garganica'' ( Apiaceae). Japan wax is a mixture containing triglycerides of C21, C22 and C23 dicarboxylic acids obtained from the sumac tree (''Rhus'' sp.). A large survey of the dicarboxylic acids present in Mediterranean nuts revealed unusual components. A total of 26 minor acids (from 2 in pecan to 8% in peanut) were determined: 8 species derived from succinic acid, likely in relation with photosynthesis, and 18 species with a chain from 5 to 22 carbon atoms. Higher weight acids (>C20) are found in suberin present at vegetal surfaces (outer bark, root epidermis). C16 to C26 a, ω-dioic acids are considered as diagnostic for suberin. With C18:1 and C18:2, their content amount from 24 to 45% of whole suberin. They are present at low levels (< 5%) in plant cutin, except in ''

Arabidopsis thaliana ''Arabidopsis thaliana'', the thale cress, mouse-ear cress or arabidopsis, is a small flowering plant native to Eurasia and Africa. ''A. thaliana'' is considered a weed; it is found along the shoulders of roads and in disturbed land. A winter a ...

'' where their content can be higher than 50%. It was shown that hyperthermophilic microorganisms specifically contained a large variety of dicarboxylic acids. This is probably the most important difference between these microorganisms and other marine bacteria. Dioic fatty acids from C16 to C22 were found in an hyperthermophilic archaeon, '' Pyrococcus furiosus''. Short and medium chain (up to 11 carbon atoms) dioic acids have been discovered in

Cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, blu ...

of the genus ''

Aphanizomenon ''Aphanizomenon'' is a genus of cyanobacteria that inhabits freshwater lakes and can cause dense blooms. They are unicellular organisms that consolidate into linear (non-branching) chains called trichomes. Parallel trichomes can then further uni ...

''. Dicarboxylic acids may be produced by ω-oxidation of fatty acids during their

catabolism Catabolism () is the set of metabolic pathways that breaks down molecules into smaller units that are either oxidized to release energy or used in other anabolic reactions. Catabolism breaks down large molecules (such as polysaccharides, lipids, ...

. It was discovered that these compounds appeared in urine after administration of tricaprin and triundecylin. Although the significance of their biosynthesis remains poorly understood, it was demonstrated that ω-oxidation occurs in rat liver but at a low rate, needs oxygen,

NADPH Nicotinamide adenine dinucleotide phosphate, abbreviated NADP or, in older notation, TPN (triphosphopyridine nucleotide), is a cofactor used in anabolic reactions, such as the Calvin cycle and lipid and nucleic acid syntheses, which require NAD ...

and

cytochrome P450 Cytochromes P450 (CYPs) are a Protein superfamily, superfamily of enzymes containing heme as a cofactor (biochemistry), cofactor that functions as monooxygenases. In mammals, these proteins oxidize steroids, fatty acids, and xenobiotics, and are ...

. It was later shown that this reaction is more important in starving or diabetic animals where 15% of palmitic acid is subjected to ω-oxidation and then tob-oxidation, this generates

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 commi ...

which is further used in saturated fatty acid synthesis. The determination of the dicarboxylic acids generated by permanganate-periodate oxidation of monoenoic fatty acids was useful to study the position of the double bond in the carbon chain.

Branched-chain dicarboxylic acids

Long-chain dicarboxylic acids containing vicinal dimethyl branching near the centre of the carbon chain have been discovered in the genus ''

Butyrivibrio ''Butyrivibrio'' is a genus of bacteria in Clostridia, Class Clostridia. Bacteria of this genus are common in the gastrointestinal systems of many animals. Genus ''Butyrivibrio'' was first described by Bryant and Small (1956) as Anaerobic organi ...

'', bacteria which participate in the digestion of cellulose in the rumen. These fatty acids, named diabolic acids, have a chain length depending on the fatty acid used in the culture medium. The most abundant diabolic acid in ''Butyrivibrio'' had a 32-carbon chain length. Diabolic acids were also detected in the core lipids of the genus '' Thermotoga'' of the order Thermotogales, bacteria living in solfatara springs, deep-sea marine hydrothermal systems and high-temperature marine and continental oil fields. It was shown that about 10% of their lipid fraction were symmetrical C30 to C34 diabolic acids. The C30 (13,14-dimethyloctacosanedioic acid) and C32 (15,16-dimethyltriacontanedioic acid) diabolic acids have been described in Thermotoga maritima. Some parent C29 to C32 diacids but with methyl groups on the carbons C-13 and C-16 have been isolated and characterized from the lipids of thermophilic anaerobic eubacterium Themanaerobacter ethanolicus. The most abundant diacid was the C30 a,ω-13,16-dimethyloctacosanedioic acid. Biphytanic diacids are present in geological sediments and are considered as tracers of past anaerobic oxidation of methane. Several forms without or with one or two pentacyclic rings have been detected in Cenozoic seep limestones. These lipids may be unrecognized metabolites from Archaea.

Crocetin Crocetin is a natural apocarotenoid dicarboxylic acid that is found in the crocus flower together with its glycoside, crocin, and '' Gardenia jasminoides'' fruits. It forms brick red crystals with a melting point of 285°C. The chemical struct ...

is the core compound of crocins (crocetin glycosides) which are the main red pigments of the stigmas of saffron ( Crocus sativus) and the fruits of gardenia (

Gardenia jasminoides ''Gardenia jasminoides'', commonly known as gardenia, is an evergreen flowering plant in the coffee family Rubiaceae. It is native to parts of South-East Asia. Wild plants range from 30 centimetres to 3 metres (about 1 to 10 feet) in height. The ...

). Crocetin is a 20-carbon chain dicarboxylic acid which is a diterpenenoid and can be considered as a carotenoid. It was the first plant carotenoid to be recognized as early as 1818 while the history of saffron cultivation reaches back more than 3,000 years. The major active ingredient of saffron is the yellow pigment

crocin Crocin is a carotenoid chemical compound that is found in the flowers of crocus and gardenia. Crocin is the chemical primarily responsible for the color of saffron. Chemically, crocin is the diester formed from the disaccharide gentiobiose and ...

2 (three other derivatives with different glycosylations are known) containing a gentiobiose (disaccharide) group at each end of the molecule. A simple and specific HPLC-UV method has been developed to quantify the five major biologically active ingredients of saffron, namely the four crocins and crocetin.

Unsaturated dicarboxylic acids

: Traumatic acid, was among the first biologically active molecules isolated from plant tissues. This dicarboxylic acid was shown to be a potent wound healing agent in plant that stimulates cell division near a wound site, it derives from 18:2 or 18:3 fatty acid hydroperoxides after conversion into oxo- fatty acids. ''trans,trans''-Muconic acid is a

metabolite In biochemistry, a metabolite is an intermediate or end product of metabolism. The term is usually used for small molecules. Metabolites have various functions, including fuel, structure, signaling, stimulatory and inhibitory effects on enzymes, c ...

of benzene in humans. The determination of its concentration in urine is therefore used as a biomarker of occupational or environmental exposure to benzene. Glutinic acid, a substituted allene, was isolated from '' Alnus glutinosa'' (Betulaceae). While polyunsaturated fatty acids are unusual in plant cuticles, a diunsaturated dicarboxylic acid has been reported as a component of the surface waxes or polyesters of some plant species. Thus, octadeca-c6,c9-diene-1,18-dioate, a derivative of linoleic acid, is present in Arabidopsis and

Brassica napus Rapeseed (''Brassica napus ''subsp.'' napus''), also known as rape, or oilseed rape, is a bright-yellow flowering member of the family Brassicaceae (mustard or cabbage family), cultivated mainly for its oil-rich seed, which naturally contains a ...

cuticle.

Alkylitaconates

] Several dicarboxylic acids having an alkyl side chain and an itaconate core have been isolated from

lichen A lichen ( , ) is a composite organism that arises from algae or cyanobacteria living among filaments of multiple fungi species in a mutualistic relationship.fungi, itaconic acid (methylenesuccinic acid) being a metabolite produced by filamentous fungi. Among these compounds, several analogues, called chaetomellic acids with different chain lengths and degrees of unsaturation have been isolated from various species of the lichen Chaetomella. These molecules were shown to be valuable as basis for the development of anticancer drugs due to their strong

farnesyltransferase Farnesyltransferase () is one of the three enzymes in the prenyltransferase group. Farnesyltransferase (FTase) adds a 15-carbon isoprenoid called a farnesyl group to proteins bearing a CaaX motif: a four-amino acid sequence at the carboxyl ter ...

inhibitory effects. A series of alkyl- and alkenyl-itaconates, known as ceriporic acids
Pub Chem 52921868
, were found in cultures of a selective

lignin Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity ...

-degrading fungus ( white rot fungus), Ceriporiopsis subvermispora. The absolute configuration of ceriporic acids, their stereoselective biosynthetic pathway and the diversity of their metabolites have been discussed in detail.

Substituted dicarboxylic acids

Aromatic dicarboxylic acids

: Terephthalic acid is a commodity chemical used in the manufacture of the

known by brand names such as PET, Terylene, Dacron and Lavsan.

Properties

Dicarboxylic acids are crystalline solids. Solubility in water and melting point of the α,ω- compounds progress in a series as the carbon chains become longer with alternating between odd and even numbers of carbon atoms, so that for even numbers of carbon atoms the melting point is higher than for the next in the series with an odd number. These compounds are weak dibasic acids with pK_a tending towards values of ca. 4.5 and 5.5 as the separation between the two carboxylate groups increases. Thus, in an aqueous solution at pH about 7, typical of biological systems, the Henderson–Hasselbalch equation indicates they exist predominantly as dicarboxylate anions. The dicarboxylic acids, especially the small and linear ones, can be used as crosslinking reagents. Dicarboxylic acids where the carboxylic groups are separated by none or one carbon atom decompose when they are heated to give off carbon dioxide and leave behind a monocarboxylic acid. Blanc's Rule says that heating a barium salt of a dicarboxylic acid, or dehydrating it with acetic anhydride will yield a cyclic acid anhydride if the carbon atoms bearing acid groups are in position 1 and (4 or 5). So succinic acid will yield succinic anhydride. For acids with carboxylic groups at position 1 and 6 this dehydration causes loss of carbon dioxide and water to form a cyclic ketone, for example, adipic acid will form cyclopentanone.

Derivatives

As for monofunctional carboxylic acids, derivatives of the same types exist. However, there is the added complication that either one or two of the carboxylic groups could be altered. If only one is changed then the derivative is termed "acid", and if both ends are altered it is called "normal". These derivatives include salts, chlorides, esters, amides, and anhydrides. In the case of anhydrides or amides, two of the carboxyl groups can come together to form a cyclic compound, for example succinimide.

References

External links

Lipidomics gateway Structure Database Dicarboxylic acids
* {{Authority control