Acetylenedicarboxylic acid

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Acetylenedicarboxylic acid [1]
Acetylenedicarboxylic acid.svg
Acetylenedicarboxylic-acid-3D-balls.png
Names
Preferred IUPAC name
But-2-ynedioic acid
Other names
2-Butynedioic acid
Identifiers
3D model (JSmol)
3DMet
878357
ChEBI
ChemSpider
ECHA InfoCard 100.005.033 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 205-536-0
26624
KEGG
PubChem CID
UNII
  • InChI=1S/C4H2O4/c5-3(6)1-2-4(7)8/h(H,5,6)(H,7,8) Yes check.svgY
    Key: YTIVTFGABIZHHX-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C4H2O4/c5-3(6)1-2-4(7)8/h(H,5,6)(H,7,8)
    Key: YTIVTFGABIZHHX-UHFFFAOYAA
  • C(#CC(=O)O)C(=O)O
  • O=C(O)C#CC(=O)O
Properties
H2C4O4
Molar mass 114.056 g·mol−1
AppearanceCrystalline solid
Melting point 175 to 176 °C (347 to 349 °F; 448 to 449 K) (decomposes) [2]
180–187 °C (decomposes) [1]
Conjugate base Hydrogen acetylenedicarboxylate (chemical formula HC4O−4)
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H301, H314, H315, H319, H335
P260, P261, P264, P270, P271, P280, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P310, P312, P321, P330, P332+P313, P337+P313, P362, P363, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Acetylenedicarboxylic acid or butynedioic acid is an organic compound (a dicarboxylic acid) with the formula H2C4O4 or HO−C(=O)−C≡C−C(=O)−OH. It is a crystalline solid that is soluble in diethyl ether.

Contents

The removal of two protons yields the acetylenedicarboxylate dianion C4O2−4, which consists only of carbon and oxygen, making it an oxocarbon anion. Partial ionization yields the monovalent hydrogen acetylenedicarboxylate anion HC4O−4.

The acid was first described in 1877 by Polish chemist Ernest Bandrowski. [2] [3] [4] It can be obtained by treating α,β-dibromosuccinic acid with potassium hydroxide KOH in methanol or ethanol. The reaction yields potassium bromide and potassium acetylenedicarboxylate. The salts are separated and the latter is treated with sulfuric acid. [2]

Acetylenedicarboxylic acid is used in the synthesis of dimethyl acetylenedicarboxylate, an important laboratory reagent. The acid is commonly traded as a laboratory chemical. It can also be reacted with sulfur tetrafluoride to produce hexafluoro-2-butyne, a powerful dienophile for use in Diels-Alder reactions.

Fatty alcohol esters of acetylenedicarboxylic acid can be used for the preparation of phase change materials (PCM). [5]

Anions and salts

Hydrogen acetylenedicarboxylate (often abbreviated as Hadc or HADC) is a monovalent anion of acetylenedicarboxylic acid with the formula HC4O−4 or HO−C(=O)−C≡C−CO−2. The anion can be derived from acetylenedicarboxylic acid by removal of a single proton or from the acetylenedicarboxylate dianion by addition of a proton. The name is also used for any salt of this anion. Salts of this anion are of interest in crystallography because they contain unusually short and strong hydrogen bonds. In many crystalline salts (with the exception of the lithium one), the HADC units form linear chains connected by strong hydrogen bonds. Each carboxylate group is usually planar; but the two groups may lie in different planes due to rotation about the carbon–carbon bonds. They are coplanar in the hydrated salts NaHC4O4·2H2O and CsHC4O4·2H2O, nearly coplanar in the guanidinium salt [C(NH2)3]+[HC4O4]−, but off by 60° or more in other salts such as anhydrous KHC4O4. [6]

Potassium hydrogen acetylenedicarboxylate is a potassium salt of HADC with chemical formula KHC4O4 or K+HC4O−4, often abbreviated as KHadc. It is often called potassium hydrogen acetylenedicarboxylate or monopotassium acetylenedicarboxylate. The salt can be obtained from acetylenedicarboxylic acid and is a common laboratory starting material for the synthesis of other derivatives of that acid. In the crystalline form, the hydrogen acetylenedicarboxylate anions are joined into linear chains by uncommonly short hydrogen bonds. [7] [8]

Chemical structure of acetylenedicarboxylate Acetylenedicarboxylate.png
Chemical structure of acetylenedicarboxylate

Acetylenedicarboxylate (often abbreviated as ADC or adc) is a divalent anion with formula C4O2−4 or [O2C−C≡C−CO2]2−; or any salt or ester thereof. The anion can be derived from acetylenedicarboxylic acid by the loss of two protons. It is one of several oxocarbon anions which, like carbonate CO2−3 and oxalate C2O2−4, consist solely of carbon and oxygen. The ADC anion can aсt as a ligand in organometallic complexes, such as the blue polymeric complex with copper(II) and 2,2′-bipyridine, [Cu2+[C4O4]2−·(C5H4N)2]n. [9] [10] Thallium(I) acetylenedicarboxylate (Tl2C4O4) decomposes at 195 °C, leaving a residue of pyrophoric thallium powder. [11]

See also

Related Research Articles

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In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is R−COOH or R−CO2H, with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

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

Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO• is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

<span class="mw-page-title-main">Bisulfide</span> Inorganic anion containing one sulfur and one hydrogen atoms

Bisulfide is an inorganic anion with the chemical formula HS−. It contributes no color to bisulfide salts, and its salts may have a distinctive putrid smell. It is a strong base. Bisulfide solutions are corrosive and attack the skin.

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

Caesium fluoride or cesium fluoride is an inorganic compound with the formula CsF and it is a hygroscopic white salt. Caesium fluoride can be used in organic synthesis as a source of the fluoride anion. Caesium also has the highest electropositivity of all known elements and fluorine has the highest electronegativity of all known elements.

<span class="mw-page-title-main">Carboxylate</span> Chemical group (RCOO); conjugate base of a carboxylic acid

In organic chemistry, a carboxylate is the conjugate base of a carboxylic acid, RCOO−. It is an ion with negative charge.

Squaric acid, also called quadratic acid because its four carbon atoms approximately form a square, is a diprotic organic acid with the chemical formula C4O2(OH)2.

<span class="mw-page-title-main">Tetrafluoroborate</span> Anion

Tetrafluoroborate is the anion BF−
4. This tetrahedral species is isoelectronic with tetrafluoroberyllate (BeF2−
4), tetrafluoromethane (CF4), and tetrafluoroammonium (NF+
4) and is valence isoelectronic with many stable and important species including the perchlorate anion, ClO−
4, which is used in similar ways in the laboratory. It arises by the reaction of fluoride salts with the Lewis acid BF3, treatment of tetrafluoroboric acid with base, or by treatment of boric acid with hydrofluoric acid.

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

Dimethyl acetylenedicarboxylate (DMAD) is an organic compound with the formula CH3O2CC2CO2CH3. It is a di-ester in which the ester groups are conjugated with a C-C triple bond. As such, the molecule is highly electrophilic, and is widely employed as a dienophile in cycloaddition reactions, such as the Diels-Alder reaction. It is also a potent Michael acceptor. This compound exists as a colorless liquid at room temperature. This compound was used in the preparation of nedocromil.

Thiocarbonate describes a family of anions with the general chemical formula CS
3−xO2−
x (x = 0, 1, or 2):

<span class="mw-page-title-main">Tetrahydroxy-1,4-benzoquinone</span> Chemical compound

Tetrahydroxy-1,4-benzoquinone, also called tetrahydroxy-p-benzoquinone, tetrahydroxybenzoquinone, or tetrahydroxyquinone, is an organic compound with formula C6O2(OH)4. Its molecular structure consists of a cyclohexadiene ring with four hydroxyl groups and two ketone groups in opposite (para) positions.

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

Deltic acid is a chemical substance with the chemical formula C3O(OH)2. It can be viewed as a ketone and double enol of cyclopropene. At room temperature, it is a stable white solid, soluble in diethyl ether, that decomposes between 140 °C and 180 °C, and reacts slowly with water.

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

Croconic acid is a chemical compound with formula C5H2O5 or (C=O)3(COH)2. It has a cyclopentene backbone with two hydroxyl groups adjacent to the double bond and three ketone groups on the remaining carbon atoms. It is sensitive to light, soluble in water and ethanol and forms yellow crystals that decompose at 212 °C.

<span class="mw-page-title-main">Oxocarbon anion</span> Negatively-charged molecule made of carbon and oxygen

In chemistry, an oxocarbon anion is a negative ion consisting solely of carbon and oxygen atoms, and therefore having the general formula C
xOn−
y for some integers x, y, and n.

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

In chemistry, peroxydicarbonate is a divalent anion with the chemical formula C
2O2−
6. It is one of the oxocarbon anions, which consist solely of carbon and oxygen. Its molecular structure can be viewed as two carbonate anions joined so as to form a peroxide bridge –O–O–.

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

In chemistry, peroxycarbonate or percarbonate is a divalent anion with formula CO2−
4. It is an oxocarbon anion that consists solely of carbon and oxygen. It would be the anion of a hypothetical peroxycarbonic acid HO–CO–O–OH. or the real hydroperoxyformic acid, HO-O-CO-OH.

<span class="mw-page-title-main">Croconate violet</span>

Croconate violet or 1,3-bis(dicyanomethylene)croconate is a divalent anion with chemical formula C
11N
4O2−
3 or ((N≡C−)2C=)2(C5O3)2−. It is one of the pseudo-oxocarbon anions, as it can be described as a derivative of the croconate oxocarbon anion C
5O2−
5 through the replacement of two oxygen atoms by dicyanomethylene groups =C(−C≡N)2. Its systematic name is 3,5-bis(dicyanomethylene)-1,2,4-trionate. The term croconate violet as a dye name specifically refers to the dipotassium salt K
2C
11N
4O
3.

<span class="mw-page-title-main">1,3-Bis(dicyanomethylene)squarate</span>

1,3-Bis(dicyanomethylene)squarate is a divalent anion with chemical formula C
10N
4O2−
2 or ((N≡C−)2C=)2(C4O2)2−. It is one of the pseudo-oxocarbon anions, as it can be described as a derivative of the squarate oxocarbon anion C
4O2−
4 through the replacement of two opposite oxygen atoms by dicyanomethylene groups =C(−C≡N)2.

<span class="mw-page-title-main">Croconate blue</span>

Croconate blue or 1,2,3-tris(dicyanomethylene)croconate is a divalent anion with chemical formula C
14N
6O2−
2 or ((N≡C−)2C=)3(C5O2)2−. It is one of the pseudo-oxocarbon anions, as it can be described as a derivative of the croconate oxocarbon anion C
5O2−
5 through the replacement of three oxygen atoms by dicyanomethylene groups =C(−C≡N)2. The term Croconate Blue as a dye name specifically refers to the dipotassium salt K
2C
14N
6O
2.

Azidotetrazolate (CN7−) is an anion which forms a highly explosive series of salts. The ion is made by removing a proton from 5-azido-1H-tetrazole. The molecular structure contains a five-membered ring with four nitrogen atoms, and an azido side chain connected to the carbon atom. Several salts exist, but they are unstable and spontaneously explode. Rubidium azidotetrazolate was so unstable that it explodes while crystallizing. The potassium and caesium salt also spontaneously explode when dry.

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

Hydromelonic acid, is an elusive chemical compound with formula C
9H
3N
13 or (HNCN)
3(C
6N
7), whose molecule would consist of a heptazine H3(C
6N
7) molecule, with three cyanamido groups H–N=C=N– or N≡C–NH– substituted for the hydrogen atoms.

References

  1. 1 2 "Acetylenedicarboxylic acid". Sigma-Aldrich.
  2. 1 2 3 Abbott, T. W.; Arnold, R. T.; Thompson, R. B. "Acetylenedicarboxylic acid". Organic Syntheses .; Collective Volume, vol. 2, p. 10
  3. ↑ Bandrowski, E. (1877). "Ueber Acetylendicarbonsäure" [On acetylenedicarboxylic acid]. Berichte der Deutschen Chemischen Gesellschaft. 10: 838–842. doi:10.1002/cber.187701001231.
  4. ↑ E. Bandrowski (1879). "Weitere Beiträge zur Kenntniss der Acetylendicarbonsäure" [Further comments on the description of acetylenedicarboxylic acid]. Berichte der Deutschen Chemischen Gesellschaft. 12 (2): 2212–2216. doi:10.1002/cber.187901202261.
  5. ↑ Daglar, Ozgun; Çakmakçı, Emrah; Hizal, Gurkan; Tunca, Umit; Durmaz, Hakan (2020-05-05). "Extremely fast synthesis of polythioether based phase change materials (PCMs) for thermal energy storage". European Polymer Journal. 130: 109681. doi:10.1016/j.eurpolymj.2020.109681. ISSN   0014-3057. S2CID   216326248.
  6. ↑ Leban, I; Rupnik, A (1992). "Structure of guanidinium hydrogen acetylenedicarboxylate, CH
    6    N+
    3    ·C
    4    HO4−
    ". Acta Crystallographica Section C. 48 (5): 821. doi:10.1107/S010827019101154X.
  7. ↑ Leban, Ivan; Golič, Ljubo; Speakman, J. Clare (1973). "Crystal structures of the acid salts of some dibasic acids. Part VII. An X-ray study of potassium hydrogen acetylenedicarboxylate: The α-form". J. Chem. Soc., Perkin Trans. 2 (6): 703–705. doi:10.1039/P29730000703.
  8. ↑ Miyakubo, Keisuke (1994). Nuclear magnetic resonance studies of dynamical structure of one-dimensional hydrogen-bonded system in the acid salts of some dicarboxylic acids (PDF) (Ph.D.). Osaka University.
  9. ↑ Li, Ming-xing; Shao, Min; Dai, Hui; An, Bao-li; Lu, Wen-cong; Zhu, Yu; Du, Chen-xia (2005). "Synthesis and Crystal Structure of a Novel Copper(II) Complex with Acetylenedicarboxylate and 2,2′-Bipyridine". Chinese Chemical Letters. 16 (10): 1405–1408.
  10. ↑ Shao, Min; Li, Ming-xing; Dai, Hui; Lu, Wen-cong; An, Bao-li (2007). "Polynuclear complexes incorporating Cu(II) and Mn(II) centers bridged by acetylenedicarboxylate: Structure, thermal stability and magnetism". Journal of Molecular Structure. 829 (1–3): 155–160. doi:10.1016/j.molstruc.2006.06.021.
  11. ↑ Ahlers, Ruth; Ruschewitz, Uwe (2009). "Non-centrosymmetric coordination polymers based on thallium and acetylenedicarboxylate". Solid State Sciences. 11 (6): 1058–1064. doi:10.1016/j.solidstatesciences.2009.03.008. S2CID   95955193.
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