Acetylacetone

Acetylacetone
Acac redirects here. For other uses, see ACAC.

Acetylacetone

Identifiers CAS number ChemSpider UNII KEGG ChEBI ChEMBL Jmol-3D images 123-54-6 29001
[2] [1] [3]

46R950BP4J C15499
[4]

CHEBI:14750

[5]

[6]

CHEMBL191625 Image 1 [8] Image 2 Properties

[7]

Molecular formula Molar mass Density Melting point Boiling point Solubility in water

C5H8O2 100.13 g/mol 0.98 g/mL 23 C 140 C 16 g/100 mL Hazards

EU Index EU classification R-phrases S-phrases NFPA 704 Flash point Autoignition temperature Explosive limits

606-029-00-0 Harmful (Xn) R10, R22 (S2), S21, S23, S24/25

34 C 340 C 2.411.6%

Acetylacetone

2
[9]

(what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25C, 100kPa)

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Infobox references

Acetylacetone is an organic compound that famously exists in two tautomeric forms that rapidly interconvert. The less stable tautomer is a diketone formally named pentane-2,4-dione. The more common tautomer is the enol form. The pair of tautomers rapidly interconvert and are treated as a single compound in most applications. It is a colourless liquid that is a precursor to acetylacetonate (acac), a common bidentate ligand. It is also a building block for the synthesis of heterocyclic compounds.

Properties
Solvent Gas Phase Kketo-enol 11.7

Cyclohexane 42 Toluene THF DMSO Water 10 7.2 2 0.23

The keto and enol forms of acetylacetone coexist in solution; these forms are tautomers. The C2v symmetry for the enol form displayed on the left in Scheme 1 has been verified by many methods, most prominently being NMR spectroscopy and IR spectroscopy.[10] In the gas phase, the equilibrium constant, Kketo-enol is 11.7, favoring the enol form.[11] The equilibrium constant tends to remain high in nonpolar solvents; the keto form becomes more favorable in polar, hydrogen-bonding solvents, such as water.[12] The enol form is a vinylogous analogue of a carboxylic acid.

Scheme 1. Tautomerism of 2,4-pentanedione

Acid-base properties
Acetylacetone is a weak acid: C5H8O2 C5H7O2 + H+

IUPAC recommended pKa values for this equilibrium in aqueous solution at 25 C are 8.990.04 (I = 0), 8.830.02 (I = 0.1 M NaClO4) and 9.000.03 (I=1.0 M NaClO4) (I=Ionic strength).[13] Values for mixed solvents are available. Very strong bases, such as organolithium compounds, will deprotonate acetylacetone twice. The resulting dilithio species can then be alkylated at C-1.

Acetylacetone

solvent

T/C pK [14] a 9.8 12.5 10.16 13.41

40% ethanol/water 30 70% dioxane/water 28 80% DMSO/water DMSO 25 25

Preparation
Acetylacetone is prepared industrially by the thermal rearrangement of isopropenylacetate.[15] CH2(CH3)COC(O)Me MeC(O)CH2C(O)Me Laboratory routes to acetylacetone begin also with acetone. Acetone and acetic anhydride upon the addition of BF3 catalyst:[16] (CH3CO)2O + CH3C(O)CH3 CH3C(O)CH2C(O)CH3 A second synthesis involves the base-catalyzed condensation of acetone and ethyl acetate, followed by acidification:[16] NaOEt + EtO2CCH3 + CH3C(O)CH3 NaCH3C(O)CHC(O)CH3 + 2 EtOH NaCH3C(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 include C6H5C(O)CH2C(O)C6H5 (dbaH) and (CH3)3CC(O)CH2C(O)CC(CH3)3. Hexafluoroacetylacetonate is also widely used to generate volatile metal complexes.

Reactions
Condensations
Acetylacetone is a versatile bifunctional precursor to heterocycles because both keto groups undergo condensation. Hydrazine reacts to produce pyrazoles. Urea gives pyrimidines. Condensation with aryl- and alkylamines to gives the mono- and then the didiketimines wherein the O atoms in acetylacetone are replaced by NR (R = aryl, alkyl).

Coordination chemistry
The acetylacetonate anion, acac-, forms complexes with many transition metal ions. A general method of synthesis is to react the metal ion with acetylacetone in the presence of a base (B): Mz+ + z (acacH) M(acac)z +z BH+

which assists the removal of a proton from acetylacetone and shifts the equilibrium in favour of the complex. 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. Since the metal complex carries no electrical charge, it is soluble in non-polar organic solvents.

A ball-and-stick model of VO(acac)2

Acetylacetone

Biodegradation
Enzymatic breakdown: The enzyme acetylacetone dioxygenase cleaves the carbon-carbon bond of acetyacetone, producing acetate and 2-oxopropanal. The enzyme is Fe(II)-dependent, but it has been proven to bind to zinc as well. Acetylacetone degradation has been characterized in the bacterium Acinetobacter johnsonii.[17] C5H8O2 + O2 C2H4O2 + C3H4O2

References
[1] [2] [3] [4] [5] [6] [7] [8] [9] http:/ / www. commonchemistry. org/ ChemicalDetail. aspx?ref=123-54-6 http:/ / www. chemspider. com/ 29001 http:/ / fdasis. nlm. nih. gov/ srs/ srsdirect. jsp?regno=46R950BP4J http:/ / www. kegg. jp/ entry/ C15499 https:/ / www. ebi. ac. uk/ chebi/ searchId. do?chebiId=14750 https:/ / www. ebi. ac. uk/ chembldb/ index. php/ compound/ inspect/ CHEMBL191625 http:/ / chemapps. stolaf. edu/ jmol/ jmol. php?model=O%3DC%28C%29CC%28%3DO%29C http:/ / chemapps. stolaf. edu/ jmol/ jmol. php?model=CC%28%3DO%29CC%28%3DO%29C http:/ / en. wikipedia. org/ wiki/ Special%3Acomparepages?rev1=443366220& page2=%3AAcetylacetone

[10] Kimberly A. Manbeck, Nicholas C. Boaz, Nathaniel C. Bair, Allix M. S. Sanders, and Anderson L. Marsh (2011). "Substituent Effects on Keto-Enol Equilibria Using NMR Spectroscopy". Journal of Chemical Education 88 (10): 14441445. doi:10.1021/ed1010932.. Z. Yoshida, H. Ogoshi, T. Tokumitsu "Intramolecular hydrogen bond in enol form of 3-substituted-2,4-pentanedione" Tetrahedron 1970, volume 26, pp. 5691-5697. doi:10.1016/0040-4020(70)80005-9 [11] W. Caminati, J.-U. Grabow (2006). "The C2v Structure of Enolic Acetylacetone". Journal of the American Chemical Society 128 (3): 854857. doi:10.1021/ja055333g. PMID16417375. [12] Solvents and Solvent Effects in Organic Chemistry, Christian Reichardt Wiley-VCH; 3 edition 2003 ISBN 3-527-30618-8 [13] Stary, J.; Liljenzin, J.O. (1982). "Critical evaluation of equilibrium constants involving acetylacetone and its metal chelates" (http:/ / www. iupac. org/ publications/ pac/ pdf/ 1982/ pdf/ 5412x2557. pdf). Pure and Applied Chemistry 54 (12): 25572592. doi:10.1351/pac198254122557. . [14] IUPAC SC-Database (http:/ / www. acadsoft. co. uk/ scdbase/ scdbase. htm) A comprehensive database of published data on equilibrium constants of metal complexes and ligands [15] Hardo Siegel, Manfred Eggersdorfer Ketones in Ullmanns Encyclopedia of Industrial Chemistry, Wiley-VCH, 2002, Wienheim. doi:10.1002/14356007.a15_077 [16] C. E. Denoon, Jr., "Acetylacetone" (http:/ / www. orgsyn. org/ orgsyn/ orgsyn/ prepContent. asp?prep=cv3p0016), Org. Synth., ; Coll. Vol. 3: 16 [17] Straganz, G.D.; Glieder, A.; Brecker, L.; Ribbons, D.W.; Steiner, W. (2003). "Acetylacetone-cleaving enzyme Dke1: a novel C-C-bond-cleaving enzyme from Acinetobacter johnsonii". Biochem. J. 369 (Pt 3): 573581. doi:10.1042/BJ20021047. PMC1223103. PMID12379146.

External links
International Chemical Safety Card 0533 (http://www.inchem.org/documents/icsc/icsc/eics0533.htm)

Article Sources and Contributors

Article Sources and Contributors

Acetylacetone Source: http://en.wikipedia.org/w/index.php?oldid=484038500 Contributors: Aegis Maelstrom, Astrochemist, Beetstra, Benjah-bmm27, Betacommand, Breakyunit, Chem-awb, Chem221, ChemicalBit, Chiu frederick, Christian75, Confiteordeo, Cwhaley, Drbreznjev, Drpagel, Dycedarg, Edgar181, Eugene-elgato, Galoubet, Grimlock, H Padleckas, Headbomb, Herbee, J. Atkinson, Japanese Searobin, Jimz0r, John of Reading, Juliancolton, Jynto, Lkinkade, Mr0t1633, Naffer, Nick Number, Petergans, Physchim62, Puppy8800, Rifleman 82, Rjwilmsi, Robertvan1, Shalom Yechiel, Silverchemist, SimonP, Smokefoot, Stone, The Other Guy, V8rik, Vijaykumarutkam, Vuo, WVhybrid, Walkerma, 35 , anonymous edits

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