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Acetylacetone is an organic compound with the chemical formula . It is a colorless liquid, classified as a 1,3- diketone. It exists in equilibrium with a tautomer . These tautomers interconvert so rapidly under most conditions that they are treated as a single compound in most applications. It is a colorless liquid that is a precursor to acetylacetonate anion (commonly abbreviated acac), a bidentate ligand. It is also a building block for the synthesis of
heterocyclic compound A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different elements as members of its ring(s). Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and ...
s.


Properties


Tautomerism

The keto and enol tautomers of acetylacetone coexist in solution. The enol form has C2v
symmetry Symmetry (from grc, συμμετρία "agreement in dimensions, due proportion, arrangement") in everyday language refers to a sense of harmonious and beautiful proportion and balance. In mathematics, "symmetry" has a more precise definit ...
, meaning the hydrogen atom is shared equally between the two oxygen atoms. In the gas phase, the equilibrium constant, ''K''keto→enol, is 11.7, favoring the enol form. The two tautomeric forms can be distinguished by NMR spectroscopy, IR spectroscopy and other methods. The equilibrium constant tends to be high in nonpolar solvents; when k = >1, the enol form is favoured. The keto form becomes more favourable in polar, hydrogen-bonding solvents, such as water. The enol form is a vinylogous analogue of a
carboxylic acid 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 or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic ...
.


Acid–base properties

Acetylacetone is a weak acid: : IUPAC recommended p''K''a values for this equilibrium in aqueous solution at 25 °C are 8.99 ± 0.04 (''I'' = 0), 8.83 ± 0.02 (''I'' = 0.1 M ) and 9.00 ± 0.03 (''I'' = 1.0 M ; ''I'' =
Ionic strength The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such as ...
). Values for mixed solvents are available. Very strong bases, such as organolithium compounds, will deprotonate acetylacetone twice. The resulting dilithium species can then be alkylated at C-1.


Preparation

Acetylacetone is prepared industrially by the thermal rearrangement of
isopropenyl acetate Isopropenyl acetate is an organic compound, which is the acetate ester of the enol tautomer of acetone. This colorless liquid is significant commercially as the principal precursor to acetylacetone. In organic synthesis, it is used to prepare en ...
. Laboratory routes to acetylacetone also begin with acetone. Acetone and
acetic anhydride Acetic anhydride, or ethanoic anhydride, is the chemical compound with the formula (CH3CO)2O. Commonly abbreviated Ac2O, it is the simplest isolable anhydride of a carboxylic acid and is widely used as a reagent in organic synthesis. It is a col ...
upon the addition of
boron trifluoride Boron trifluoride is the inorganic compound with the formula BF3. This pungent, colourless, and toxic gas forms white fumes in moist air. It is a useful Lewis acid and a versatile building block for other boron compounds. Structure and bondin ...
() catalyst: : A second synthesis involves the base-catalyzed condensation of acetone and ethyl acetate, followed by acidification: : : Because of the ease of these syntheses, many analogues of acetylacetonates are known. Some examples include
benzoylacetone Benzoylacetone is the organic compound with the nominal formula C6H5C(O)CH2C(O)CH3. As a 1,3-dicarbonyl, it is a precursor to many heterocycles, such as pyrazoles. It exists predominantly as the enol In organic chemistry, alkenols (shortened ...
, dibenzoylmethane (dbaH) and tert-butyl analogue tetramethyl-3,5-heptanedione.
Trifluoroacetylacetone 1,1,1-Trifluoroacetylacetone is the organofluorine compound with the formula CFC(O)CHC(O)CH. It is a colorless liquid. Like other 1,3-diketones, it is used as a precursor to heterocycles, e.g. pyrazoles, and metal acetylacetonates, metal chelates. ...
and
hexafluoroacetylacetonate Hexafluoroacetylacetone is the chemical compound with the nominal Chemical formula, formula CF3C(O)CH2C(O)CF3 (often abbreviated as hfacH). This colourless liquid is a ligand precursor and a reagent used in MOCVD. The compound exists exclusively ...
are also used to generate volatile metal complexes.


Reactions


Condensations

Acetylacetone is a versatile bifunctional precursor to heterocycles because both keto groups undergo
condensation Condensation is the change of the state of matter from the gas phase into the liquid phase, and is the reverse of vaporization. The word most often refers to the water cycle. It can also be defined as the change in the state of water vapor to ...
.
Hydrazine Hydrazine is an inorganic compound with the chemical formula . It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour. Hydrazine is highly toxic unless handled in solution as, for example, hydrazine ...
reacts to produce pyrazoles. Urea gives
pyrimidine Pyrimidine (; ) is an aromatic, heterocyclic, organic compound similar to pyridine (). One of the three diazines (six-membered heterocyclics with two nitrogen atoms in the ring), it has nitrogen atoms at positions 1 and 3 in the ring. The other ...
s. Condensation with two aryl- and alkylamines to gives NacNacs, wherein the oxygen atoms in acetylacetone are replaced by NR (R = aryl, alkyl).


Coordination chemistry

Sodium acetylacetonate Sodium acetylacetonate is an organic compound with the nominal formula Na
H(C(O)CH3)2 H, or h, is the eighth letter in the Latin alphabet, used in the modern English alphabet, the alphabets of other western European languages and others worldwide. Its name in English is ''aitch'' (pronounced , plural ''aitches''), or regi ...
This white, water-soluble solid is the conjugate base of acetylacetone. Preparation The compound is prepared by deprotonation of acetylacetone: :NaOH + CH ...
, Na(acac), is the precursor to many
acetylacetonate complex Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion () and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal t ...
es. A general method of synthesis is to treat a metal salt with acetylacetone in the presence of a base: : Both oxygen atoms bind to the metal to form a six-membered chelate ring. In some cases the
chelate effect Chelation is a type of bonding of ions and molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These ligands are ...
is so strong that no added base is needed to form the complex.


Biodegradation

The enzyme acetylacetone dioxygenase cleaves the carbon-carbon bond of acetylacetone, producing acetate and
2-oxopropanal Methylglyoxal (MGO) is the organic compound with the formula CH3C(O)CHO. It is a reduced derivative of pyruvic acid. It is a reactive compound that is implicated in the biology of diabetes. Methylglyoxal is produced industrially by degradatio ...
. The enzyme is iron(II)-dependent, but it has been proven to bind to zinc as well. Acetylacetone degradation has been characterized in the bacterium ''
Acinetobacter johnsonii ''Acinetobacter calcoaceticus'' is a bacterial species of the genus ''Acinetobacter''. It is a nonmotile, Gram-negative coccobacillus. It grows under aerobic conditions, is catalase positive and oxidase negative. ''A. calcoaceticus'' is a part ...
''. :


References


External links

*{{ICSC, 0533, 05 Diketones Chelating agents Ligands 3-Hydroxypropenals Enols