Dicarboxylic acid

Source: Wikipedia, the free encyclopedia.

In

aliphatic or aromatic. In general, dicarboxylic acids show similar chemical behavior and reactivity to monocarboxylic acids
.

Dicarboxylic acids are used in the preparation of

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

Linear and cyclic saturated dicarboxylic acids

The general formula for acyclic dicarboxylic acid is HO
2C(CH
2)
nCO
2H.[1] 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!'.

n Common name Systematic IUPAC name Structure pKa1 pKa2 PubChem
0 Oxalic acid ethanedioic acid 1.27 4.27 971
1 Malonic acid propanedioic acid 2.85 5.05 867
2 Succinic acid butanedioic acid 4.21 5.41 1110
3 Glutaric acid pentanedioic acid 4.34 5.41 743
4 Adipic acid hexanedioic acid 4.41 5.41 196
5 Pimelic acid heptanedioic acid 4.50 5.43 385
6 Suberic acid octanedioic acid 4.526 5.498 10457
6 1,4-Cyclohexanedicarboxylic acid 14106
7 Azelaic acid nonanedioic acid 4.550 5.498 2266
8 Sebacic acid decanedioic acid 4.720 5.450 5192
9 undecanedioic acid 15816
10 dodecanedioic acid 12736
11 Brassylic acid tridecanedioic acid 10458
14 Thapsic acid hexadecanedioic acid 10459
19 Japanic acid heneicosanedioic acid 9543668
20 Phellogenic acid docosanedioic acid 244872
28 Equisetolic acid triacontanedioic acid 5322010

Occurrence

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.[6] 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 where their content can be higher than 50%.[7]

It was shown that

hyperthermophilic microorganisms specifically contained a large variety of dicarboxylic acids.[8]
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 of the genus Aphanizomenon.[9]

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

malonyl-coA which is further used in saturated fatty acid synthesis.[10]
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.[11]

Branched-chain dicarboxylic acids

Long-chain dicarboxylic acids containing

Thermotogales, bacteria living in solfatara springs, deep-sea marine hydrothermal systems and high-temperature marine and continental oil fields.[13] 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.[14]

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 bacterium Thermoanaerobacter ethanolicus.[15] 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.[16] 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 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). 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 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.[17]

Unsaturated dicarboxylic acids

Main articles: Maleic acid and Fumaric acid
See also:
E-Z notation
Type Common name IUPAC name Isomer Structural formula PubChem
Monounsaturated Maleic acid (Z)-Butenedioic acid cis 444266
Fumaric acid (E)-Butenedioic acid trans 444972
Acetylenedicarboxylic acid But-2-ynedioic acid not applicable 371
Glutaconic acid (Z)-Pent-2-enedioic acid cis 5370328
(E)-Pent-2-enedioic acid trans 5280498
2-Decenedioic acid trans 6442613
Traumatic acid Dodec-2-enedioic acid trans 5283028
Diunsaturated Muconic acid (2E,4E)-Hexa-2,4-dienedioic acid trans,trans 5356793
(2Z,4E)-Hexa-2,4-dienedioic acid cis,trans 280518
(2Z,4Z)-Hexa-2,4-dienedioic acid cis,cis 5280518
Glutinic acid
(Allene-1,3-dicarboxylic acid)		 (RS)-Penta-2,3-dienedioic acid HO2CCH=C=CHCO2H 5242834
Branched Citraconic acid (2Z)-2-Methylbut-2-enedioic acid cis HO2CCH=C(CH3)CO2H 643798
Mesaconic acid (2E)-2-Methyl-2-butenedioic acid trans HO2CCH=C(CH3)CO2H 638129
Itaconic acid 2-Methylidenebutanedioic acid – 811

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,[18] it derives from 18:2 or 18:3 fatty acid hydroperoxides after conversion into oxo- fatty acids.

trans,trans-Muconic acid is a metabolite of benzene in humans. The determination of its concentration in urine is therefore used as a biomarker of occupational or environmental exposure to benzene.[19][20]

Glutinic acid, a substituted

allene, was isolated from Alnus glutinosa (Betulaceae).[21]

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

Brassica napus cuticle.[22]

Alkylitaconates

Itaconic acid
PubChem 811

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

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 inhibitory effects.[23]

A series of alkyl- and alkenyl-itaconates, known as ceriporic acids (Pub Chem 52921868), were found in cultures of a selective lignin-degrading fungus (white rot fungus), Ceriporiopsis subvermispora.[24][25] The absolute configuration of ceriporic acids, their stereoselective biosynthetic pathway and the diversity of their metabolites have been discussed in detail.[26]

Substituted dicarboxylic acids

Common name IUPAC name Structural formula PubChem
Tartronic acid 2-Hydroxypropanedioic acid 45
Mesoxalic acid Oxopropanedioic acid 10132
Malic acid Hydroxybutanedioic acid 525
Tartaric acid 2,3-Dihydroxybutanedioic acid 875
Oxaloacetic acid Oxobutanedioic acid 970
Aspartic acid 2-Aminobutanedioic acid 5960
dioxosuccinic acid dioxobutanedioic acid 82062
α-hydroxyGlutaric acid
 2-hydroxypentanedioic acid 43
Arabinaric acid 2,3,4-Trihydroxypentanedioic acid 109475
Acetonedicarboxylic acid 3-Oxopentanedioic acid 68328
α-Ketoglutaric acid 2-Oxopentanedioic acid 51
Glutamic acid 2-Aminopentanedioic acid 611
Diaminopimelic acid (2R,6S)-2,6-Diaminoheptanedioic acid 865
Saccharic acid (2S,3S,4S,5R)-2,3,4,5-Tetrahydroxyhexanedioic acid 33037

Aromatic dicarboxylic acids

Common names IUPAC name Structure PubChem
Phthalic acid
o-phthalic acid		 Benzene-1,2-dicarboxylic acid 1017
Isophthalic acid
m-phthalic acid		 Benzene-1,3-dicarboxylic acid 8496
Terephthalic acid
p-phthalic acid		 Benzene-1,4-dicarboxylic acid 7489
Diphenic acid
Biphenyl-2,2′-dicarboxylic acid		 2-(2-Carboxyphenyl)benzoic acid 10210
2,6-Naphthalenedicarboxylic acid 2,6-Naphthalenedicarboxylic acid 14357

Terephthalic acid is a

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.[27] These compounds are weak dibasic acids with pKa 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.[28] 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.[27]

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.[27]

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.[29]

See also

References

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External links

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