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Revision as of 19:57, 16 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 473754783 of page Acetylacetone for the Chem/Drugbox validation project (updated: '').  Latest revision as of 15:33, 21 December 2024 edit Preimage (talk | contribs)Extended confirmed users913 edits Minor copyediting 
Line 1: Line 1:
{{redirect|Acac|other uses|ACAC (disambiguation)}}
{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
{{chembox {{Chembox
| Watchedfields = changed
| verifiedrevid = 443366220
| verifiedrevid = 477240155
| ImageFile = AcacH.png
| ImageFile = Acetyloaceton.svg
| ImageSize = 260px
| ImageSize = 150px
| ImageName = Skeletal structures of both tautomers | ImageName = Skeletal structures of both tautomers
| ImageFileL1 = Acetylacetone-enol-3D-balls.png | ImageFileL1 = Acetylacetone-enol-tautomer-from-xtal-Mercury-3D-balls.png
| ImageSizeL1 = 130px
| ImageNameL1 = Ball-and-stick model of the enol tautomer | ImageNameL1 = Ball-and-stick model of the enol tautomer
| ImageFileR1 = Acetylacetone-keto-3D-balls.png | ImageFileR1 = Acetylacetone-keto-tautomer-from-xtal-Mercury-3D-balls.png
| ImageSizeR1 = 130px
| ImageNameR1 = Ball-and-stick model of the keto tautomer | ImageNameR1 = Ball-and-stick model of the keto tautomer
| ImageFileL2 = Acetylacetone-enol-tautomer-from-xtal-Mercury-3D-sf.png
|IUPACName=Pentane-2,4-dione
| ImageNameL2 = Space-filling model of the enol tautomer
|OtherNames=Hacac
| ImageFileR2 = Acetylacetone-keto-tautomer-from-xtal-Mercury-3D-sf.png
|Section1={{Chembox Identifiers
| ImageNameR2 = Space-filling model of the keto tautomer
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| IUPACName = (3Z)-4-Hydroxy-3-penten-2-one ''(enol form)''<br>Pentane-2,4-dione ''(keto form)''
| OtherNames = {{ubl|Hacac|2,4-Pentanedione}}
| Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 29001 | ChemSpiderID = 29001
| KEGG_Ref = {{keggcite|correct|kegg}} | KEGG_Ref = {{keggcite|correct|kegg}}
Line 20: Line 23:
| InChI = 1/C5H8O2/c1-4(6)3-5(2)7/h3H2,1-2H3 | InChI = 1/C5H8O2/c1-4(6)3-5(2)7/h3H2,1-2H3
| InChIKey = YRKCREAYFQTBPV-UHFFFAOYAO | InChIKey = YRKCREAYFQTBPV-UHFFFAOYAO
| SMILES1 = CC(=O)CC(=O)C
| ChEMBL_Ref = {{ebicite|correct|EBI}} | ChEMBL_Ref = {{ebicite|correct|EBI}}
| ChEMBL = 191625 | ChEMBL = 191625
Line 29: Line 31:
| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| CASNo=123-54-6 | CASNo=123-54-6
| UNII_Ref = {{fdacite|correct|FDA}} | UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 46R950BP4J | UNII = 46R950BP4J
| ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 14750 | ChEBI = 14750
| PubChem = 31261
| RTECS = SA1925000
| UNNumber = 2310
| Beilstein = 741937
| Gmelin = 2537
| EINECS = 204-634-0
| SMILES = O=C(C)CC(=O)C | SMILES = O=C(C)CC(=O)C
| SMILES1 = CC(=O)CC(=O)C
| SMILES2 = CC(O)=CC(=O)C
| SMILES2_Comment = ]
}}
| Section4 = {{Chembox Properties
| C=5|H=8|O=2
| Appearance = Colorless liquid
| Density = 0.975 g/mL<ref>{{cite web|url=http://www.sigmaaldrich.com/catalog/product/sial/05581?lang=en&region=GB|website=Sigma-Aldrich|title=05581: Acetylacetone}}</ref>
| MeltingPtC = −23
| BoilingPtC = 140
| Solubility = 16 g/(100 mL)
| Solvent = Water
| MagSus = −54.88·10<sup>−6</sup> cm<sup>3</sup>/mol
}}
| Section5 = {{Chembox Hazards
| NFPA-H = 2
| NFPA-F = 2
| NFPA-R = 0
| GHSPictograms = {{GHS02}}{{GHS06}}{{GHS07}}{{GHS08}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|226|302|311|320|331|335|341|370|412}}
| PPhrases = {{P-phrases|201|202|210|233|240|241|242|243|260|261|264|270|271|273|280|281|301+312|302+352|303+361+353|304+340|305+351+338|307+311|308+313|311|312|321|322|330|337+313|361|363|370+378|403+233|403+235|405|501}}
| FlashPtC = 34
| AutoignitionPtC = 340
| ExploLimits = 2.4–11.6%
}}
}} }}

|Section4={{Chembox Properties
'''Acetylacetone''' is an ] with the chemical formula {{chem2|CH3\sC(\dO)\sCH2\sC(\dO)\sCH3}}. It is classified as a 1,3-]. It exists in equilibrium with a ] {{chem2|CH3\sC(\dO)\sCH\dC(\sOH)\sCH3}}. The mixture is a colorless liquid. These tautomers interconvert so rapidly under most conditions that they are treated as a single compound in most applications.<ref>{{cite encyclopedia|title=2,4-Pentanedione|encyclopedia= e-EROS Encyclopedia of Reagents for Organic Synthesis|author=Thomas M. Harris|doi=10.1002/047084289X.rp030|year=2001|isbn= 0471936235}}</ref> Acetylacetone is a building block for the synthesis of many ]es as well as ]s.
|Formula=C<sub>5</sub>H<sub>8</sub>O<sub>2</sub>

|MolarMass=100.13 g/mol
==Properties==
|Density=0.98 g/mL

|MeltingPt=−23 °C
=== Tautomerism ===
|BoilingPt=140 °C
{| class="wikitable" style="float: left; margin: 1em;"
|Solubility=16 g/100 mL
|-
|Solvent=Water}
! Solvent !! ''K''<sub>keto→enol</sub>
pKa=9 in water<ref name="Evan's pKa table">Evan's pKa table</ref>
|-
pKa=13.3 in DMSO<ref name="Evan's pKa table"/>
| ] || 11.7
}}
|-
|Section15={{Chembox Hazards
| ] || 42
|EUClass=Harmful ('''Xn''')
|-
|EUIndex=606-029-00-0
| ] || 10
|NFPA-H=2
|-
|NFPA-F=2
| ] || 7.2
|NFPA-R=0
|-
|RPhrases={{R10}}, {{R22}}
| ]<ref>{{cite journal |last1=Smith |first1=Kyle T. |last2=Young |first2=Sherri C. |last3=DeBlasio |first3=James W. |last4=Hamann |first4=Christian S. |title=Measuring Structural and Electronic Effects on Keto–Enol Equilibrium in 1,3-Dicarbonyl Compounds |journal=Journal of Chemical Education |date=12 April 2016 |volume=93 |issue=4 |pages=790–794 |doi=10.1021/acs.jchemed.5b00170|bibcode=2016JChEd..93..790S }}</ref> || 5.7
|SPhrases={{S2}}, {{S21}}, {{S23}}, {{S24/25}}
|-
|FlashPt=34 °C
| ] || 2
|Autoignition=340 °C
|-
|ExploLimits=2.4–11.6%
| ] || 0.23
}}
} |}

]
The ] ] of acetylacetone coexist in solution. The enol form has C<sub>2v</sub> ], meaning the hydrogen atom is shared equally between the two oxygen atoms.<ref>{{cite journal
|title=The C<sub>2v</sub> Structure of Enolic Acetylacetone
|first1=W.|last1=Caminati|first2=J.-U.|last2=Grabow|year=2006
|journal=]|volume=128|issue=3|pages=854–857|doi=10.1021/ja055333g|pmid=16417375
}}</ref> In the gas phase, the ], ''K''<sub>keto→enol</sub>, is 11.7, favoring the enol form. The two tautomeric forms can be distinguished by ], ] and other methods.<ref>{{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=]|volume=88|issue=10|pages=1444–1445|doi=10.1021/ed1010932
|bibcode=2011JChEd..88.1444M}}</ref><ref>{{cite journal
|title=Intramolecular hydrogen bond in enol form of 3-substituted-2,4-pentanedione|journal=]|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}}</ref>

The equilibrium constant tends to be high in nonpolar solvents; when ''K''<sub>keto→enol</sub> 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.<ref>{{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}}</ref> The enol form is a ] analogue of a ].{{citation needed|date=May 2024}}{{clear|left}}

=== Acid–base properties ===
{| class="wikitable" style="float: left; margin: 1em;"
|-
!Solvent!!T/°C!!p''K''<sub>a</sub><ref name=scdb> {{Webarchive|url=https://web.archive.org/web/20170619235720/http://www.acadsoft.co.uk/scdbase/scdbase.htm |date=2017-06-19}} A comprehensive database of published data on equilibrium constants of metal complexes and ligands</ref>
|-
|40% ]/water||30||9.8
|-
|70% ]/water||28||12.5
|-
|80% ]/water||25||10.16
|-
|DMSO||25||13.41
|}

Acetylacetone is a ]. It forms the acetylacetonate ] {{chem2|C5H7O2−}} (commonly abbreviated '''{{chem2|acac−}}'''):
:{{chem2|C5H8O2 ⇌ C5H7O2− + H+}}
]
In the acetylacetonate anion, both ]-] bonds are equivalent. Both C-C central bonds are equivalent as well, with one ] atom bonded to the central carbon atom (the ]). Those two equivalencies are because there is a ] between the four bonds in the ] in the acetylacetonate anion, where the ] of those four bonds is about 1.5. Both ] atoms equally share the ]. The acetylacetonate anion is a ] ].
] recommended ] values for this equilibrium in aqueous solution at 25&nbsp;°C are 8.99&nbsp;±&nbsp;0.04 (''I''&nbsp;= 0), 8.83&nbsp;±&nbsp;0.02 (''I''&nbsp;= 0.1&nbsp;] ]) and 9.00&nbsp;±&nbsp;0.03 (''I''&nbsp;= 1.0&nbsp;M {{chem2|NaClO4}}; ''I''&nbsp;= ]).<ref>{{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}}</ref> Values for mixed solvents are available. Very strong ], such as ] compounds, will ] acetylacetone twice. The resulting dilithium species can then be ] at the ] atom at the ].{{clear|left}}

==Preparation==
Acetylacetone is prepared industrially by the thermal rearrangement of ].<ref>{{cite encyclopedia|encyclopedia=]|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 }}</ref>

]

Laboratory routes to acetylacetone also begin with ]. Acetone and ] ({{chem2|(CH3C(O))2O}}) upon the addition of ] ({{chem2|BF3}}) catalyst:<ref name = denoon>{{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}}</ref>
:{{chem2|(CH3C(O))2O + CH3C(O)CH3 → CH3C(O)CH2C(O)CH3}}

A second synthesis involves the base-catalyzed condensation (e.g., by ] {{chem2|CH3CH2O-Na+}}) of acetone and ], followed by acidification of the ] (e.g., by ] HCl):<ref name = denoon/>
:{{chem2|CH3CH2O-Na+ + CH3C(O)OCH2CH3 + CH3C(O)CH3 → Na+ + 2 CH3CH2OH}}
:{{chem2|Na+ + HCl → CH3C(O)CH2C(O)CH3 + NaCl}}

Because of the ease of these syntheses, many analogues of acetylacetonates are known. Some examples are ], ] (dbaH){{clarify|reason=The abbreviation for dibenzoylmethane is "DBM", not "dbaH". Am I missing something?|date=November 2023}} and ] analogue ]. ] and ] are also used to generate volatile ]es.

==Reactions==

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

===Coordination chemistry===
{{main article|Metal acetylacetonates}}
] of VO(acac)<sub>2</sub>]]
], Na(acac), is the precursor to many ]es. A general method of synthesis is to treat a metal salt with acetylacetone in the presence of a ]:<ref>{{cite web|url=http://homepages.gac.edu/~bobrien/Inorganic_Lab/acac/Co.tfa.3.&.Co.acac.3.handout.S01.pdf|title=Co(tfa)<sub>3</sub> & Co(acac)<sub>3</sub> handout|first=Brian|last= O'Brien|publisher= Gustavus Adolphus College}}</ref>
:{{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 ] is so strong that no added base is needed to form the complex.

==Biodegradation==
The enzyme ] cleaves a central carbon-carbon bond of acetylacetone, producing acetate and ]. The enzyme is ]-dependent, but it has been proven to bind to ] as well. Acetylacetone degradation has been characterized in the bacterium '']''.<ref>{{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}}</ref>
:{{chem2|CH3C(O)CH2C(O)CH3 + ] → ] + ]}}

==References==
{{Reflist}}

==External links==
*{{ICSC|0533|05}}

{{Acetylacetonate complexes}}

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