acetylacetone

File:Acetylaceton-Tautomerie.svg

The keto and enol tautomers of acetylacetone coexist in solution. The enol form has C_2v symmetry, meaning the hydrogen atom is shared equally between the two oxygen atoms.{{cite journal

|title=The C_2v Structure of Enolic Acetylacetone

|first1=W.|last1=Caminati|first2=J.-U.|last2=Grabow|year=2006

|journal=Journal of the American Chemical Society|volume=128|issue=3|pages=854–857|doi=10.1021/ja055333g|pmid=16417375

}} 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.{{cite journal

|title=Substituent Effects on Keto–Enol Equilibria Using NMR Spectroscopy

|first1=Kimberly A.|last1=Manbeck|first2=Nicholas C.|last2=Boaz|first3=Nathaniel C.|last3=Bair|first4=Allix M. S.|last4=Sanders|first5=Anderson L.|last5=Marsh|year=2011

|journal=Journal of Chemical Education|volume=88|issue=10|pages=1444–1445|doi=10.1021/ed1010932

|bibcode=2011JChEd..88.1444M}}{{cite journal

|title=Intramolecular hydrogen bond in enol form of 3-substituted-2,4-pentanedione|journal=Tetrahedron|year=1970|volume=26|issue=24|pages=5691–5697|doi=10.1016/0040-4020(70)80005-9|first1=Z.|last1=Yoshida|first2=H.|last2=Ogoshi|first3=T.|last3=Tokumitsu}}

The equilibrium constant tends to be high in nonpolar solvents; when K_keto→enol is equal or greater than 1, the enol form is favoured. The keto form becomes more favourable in polar, hydrogen-bonding solvents, such as water.{{cite book|title=Solvents and Solvent Effects in Organic Chemistry|first=Christian|last=Reichardt|publisher=Wiley-VCH|edition= 3rd|date= 2003|isbn=3-527-30618-8}} The enol form is a vinylogous analogue of a carboxylic acid.{{citation needed|date=May 2024}}{{clear|left}}

Acetylacetone is a weak acid. It forms the acetylacetonate anion {{chem2|C5H7O2−}} (commonly abbreviated {{chem2|acac−}}):

{{block indent|{{chem2|C5H8O2 ⇌ C5H7O2− + H+}}}}

File:Acetylacetonate anion.png

In the acetylacetonate anion, both {{chem2|C\sO}} bonds are equivalent. Both {{chem2|C\sC}} central bonds are equivalent as well, with one hydrogen atom bonded to the central carbon atom (the atom numbered C3 according to the IUPAC nomenclature of organic chemistry). These equivalencies are because there is a resonance between the four bonds in the O−C2−C3−C4−O linkage in the acetylacetonate anion. Each of the four bonds in the linkage has a bond order of about 1.5, and the two oxygen atoms equally share the negative charge. The acetylacetonate anion is a bidentate ligand.

IUPAC recommended pK_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 Sodium perchlorate) and 9.00 ± 0.03 (I = 1.0 M {{chem2|NaClO4}}; I = Ionic strength).{{cite journal|last1=Stary|first1=J.|last2=Liljenzin|author2-link=Jan-Olov Liljenzin|first2= J. O.|year=1982|title=Critical evaluation of equilibrium constants involving acetylacetone and its metal chelates|volume=54|issue=12|pages=2557–2592| doi=10.1351/pac198254122557| url=http://www.iupac.org/publications/pac/pdf/1982/pdf/5412x2557.pdf|journal=Pure and Applied Chemistry|s2cid=96848983}} 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 the carbon atom at the position 1.{{clear|left}}

Acetylacetone is prepared industrially by the thermal rearrangement of isopropenyl acetate.{{cite encyclopedia|encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry|location=Weinheim |publisher=Wiley-VCH |first1=Hardo|last1=Siegel|first2=Manfred|last2=Eggersdorfer|chapter=Ketones|doi=10.1002/14356007.a15_077|date=2002|isbn=9783527306732 }}

File:Acetylacetone synthesis01.svg

Laboratory routes to acetylacetone also begin with acetone. Acetone and acetic anhydride ({{chem2|(CH3C(O))2O}}) upon the addition of boron trifluoride ({{chem2|BF3}}) catalyst:{{OrgSynth | title = Acetylacetone | first1 = C. E. Jr. |last1 =Denoon | first2 =Homer| last2 =Adkins| first3 =James L.| last3 =Rainey | volume = 20 | page = 6 | doi = 10.15227/orgsyn.020.0006|year=1940}}

{{block indent|{{chem2|(CH3C(O))2O + CH3C(O)CH3 → CH3C(O)CH2C(O)CH3}}}}

A second synthesis involves the base-catalyzed condensation (e.g., by sodium ethoxide {{chem2|CH3CH2O-Na+}}) of acetone and ethyl acetate, followed by acidification of the sodium acetylacetonate (e.g., by hydrogen chloride HCl):

{{block indent|{{chem2|CH3CH2O-Na+ + CH3C(O)OCH2CH3 + CH3C(O)CH3 → Na+[CH3C(O)CHC(O−)CH3] + 2 CH3CH2OH}}}}

{{block indent|{{chem2|Na+[CH3C(O)CHC(O−)CH3] + HCl → CH3C(O)CH2C(O)CH3 + NaCl}}}}

Because of the ease of these syntheses, many analogues of acetylacetonates are known. Some examples are benzoylacetone, dibenzoylmethane and tert-butyl analogue 2,2,6,6-tetramethyl-3,5-heptanedione. Trifluoroacetylacetone and hexafluoroacetylacetonate are also used to generate volatile metal complexes.

Acetylacetone is a versatile bifunctional precursor to heterocycles because both keto groups may undergo condensation. For example, condensation with hydrazine produces pyrazoles while condensation with urea provides pyrimidines. Condensation with two aryl- or alkylamines gives NacNacs, wherein the oxygen atoms in acetylacetone are replaced by NR (R = aryl, alkyl).

{{main article|Metal acetylacetonates}}

Image:Vanadyl-acetylacetonate-from-xtal-3D-balls.png of VO(acac)₂]]

Sodium acetylacetonate, Na(acac), is the precursor to many acetylacetonate complexes. A general method of synthesis is to treat a metal salt with acetylacetone in the presence of a base:{{cite web|url=http://homepages.gac.edu/~bobrien/Inorganic_Lab/acac/Co.tfa.3.&.Co.acac.3.handout.S01.pdf|title=Co(tfa)₃ & Co(acac)₃ handout|first=Brian|last= O'Brien|publisher= Gustavus Adolphus College}}

:{{chem2|MB_{z} + z Hacac <-> M(acac)_{z} + z BH}}

Both oxygen atoms bind to the metal to form a six-membered chelate ring. In some cases the chelate effect is so strong that no added base is needed to form the complex.

The enzyme acetylacetone dioxygenase cleaves a central carbon-carbon bond of acetylacetone, producing acetate and 2-oxopropanal. 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.{{cite journal|last1=Straganz|first1=G.D.|last2=Glieder|first2=A.|last3=Brecker|first3=L.|last4=Ribbons|first4=D.W.|last5=Steiner|first5=W.|year=2003|title=Acetylacetone-cleaving enzyme Dke1: a novel C–C-bond-cleaving enzyme from Acinetobacter johnsonii|journal= Biochemical Journal|pmid=12379146|volume=369|issue=3|pmc=1223103|pages=573–581|doi=10.1042/BJ20021047}}

:{{chem2|CH3C(O)CH2C(O)CH3 + O2 → CH3COOH + CH3C(O)CHO}}

{{Reflist}}

• {{ICSC|0533|05}}

{{Acetylacetonate complexes}}

Category:Diketones

Category:Chelating agents

Category:Ligands

Category:3-Hydroxypropenals

Category:Enols