:Acetoacetanilide
{{Chembox
| ImageFile = Acetoacetanilide.svg
| ImageSize = 150px
| ImageAlt =
| PIN = 3-Oxo-N-phenylbutanamide
| OtherNames = Acetoacetylaminobenzene
| Section1 = {{Chembox Identifiers
| CASNo = 102-01-2
| CASNo_Ref = {{cascite|correct|}}
| EC_number = 202-996-4
| ChEMBL = 1604429
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = W35JB9PY3X
| PubChem = 7592
| ChemSpiderID = 7311
| SMILES = CC(=O)CC(=O)NC1=CC=CC=C1
| InChI = 1/C10H11NO2/c1-8(12)7-10(13)11-9-5-3-2-4-6-9/h2-6H,7H2,1H3,(H,11,13)
| InChIKey = DYRDKSSFIWVSNM-UHFFFAOYAR
| StdInChI = 1S/C10H11NO2/c1-8(12)7-10(13)11-9-5-3-2-4-6-9/h2-6H,7H2,1H3,(H,11,13)
| StdInChIKey = DYRDKSSFIWVSNM-UHFFFAOYSA-N}}
| Section2 = {{Chembox Properties
| C=10|H=11|N=1|O=2
| Appearance = Colourless solid
| Density =
| MeltingPtC = 83 to 88
| BoilingPt =
| Solubility = low}}
| Section3 = {{Chembox Hazards
| GHSPictograms = {{GHS07}}{{GHS08}}
| GHSSignalWord = Warning
| HPhrases = {{H-phrases|302|312|332|373}}
| PPhrases = {{P-phrases|260|261|264|270|271|280|301+312|302+352|304+312|304+340|312|314|322|330|363|501}}
| NFPA-H=2
| NFPA-F=1
| NFPA-R=0
| MainHazards =
| FlashPt =
| AutoignitionPt = }}
}}
Acetoacetanilide is an organic compound with the formula CH3C(O)CH2C(O)NHC6H5. It is the acetoacetamide derivative of aniline. It is a white solid that is poorly soluble in water. This chemical and many related compounds (prepared from various aniline derivatives) are used in the production of organic pigments called arylide yellows, one example being Pigment Yellow 74.
Structure
Acetoacetanilide crystallizes as the keto-amide tautomer according to X-ray crystallography. The molecules are linked by intermolecular hydrogen bonds, which allows the benzoyl ketone to rotate out of the plane of the amide.{{cite journal |doi=10.1021/ja000921+ |date=2000 |volume=122 |issue=42 |last1=Gilli |first1=Paola |last2=Bertolasi |first2=Valerio |last3=Ferretti |first3=Valeria |last4=Gilli |first4=Gastone |title=Evidence for Intramolecular N−H···O Resonance-Assisted Hydrogen Bonding in β-Enaminones and Related Heterodienes. A Combined Crystal-Structural, IR and NMR Spectroscopic, and Quantum-Mechanical Investigation |journal=Journal of the American Chemical Society |page=10405 |bibcode=2000JAChS.12210405G }} For the general case of substituted acetoanilides, substituents on the aryl ring affect the balance of intra- vs intermolecular hydrogen bonding.{{cite journal |doi=10.1246/bcsj.65.3234 |title=Crystal and Molecular Structures of Acetoacetanilide, and o - and p -Chloroacetoacetanilides: X-Ray Crystallographic and MO Study |date=1992 |last1=Kubozono |first1=Yoshihiro |last2=Kohno |first2=Isao |last3=Ooishi |first3=Kazuo |last4=Namazue |first4=Sakuhiro |last5=Haisa |first5=Masao |last6=Kashino |first6=Setsuo |journal=Bulletin of the Chemical Society of Japan |volume=65 |issue=12 |pages=3234–3240 }} The situation is illustrated by the 2' vs. 3' vs. 4' fluoro-substituted acetoacetanilides.{{cite journal |doi=10.1107/S0108270102016086 |title=Structural motifs in acetoacetanilides: The effect of a fluorine substituent |date=2002 |last1=Chisholm |first1=Greig |last2=Kennedy |first2=Alan R. |last3=Beaton |first3=Laura |last4=Brook |first4=Eve |journal=Acta Crystallographica Section C Crystal Structure Communications |volume=58 |issue=11 |pages=o645–o648 |pmid=12415169 |bibcode=2002AcCrC..58O.645C }}
Preparation and reactions
Acetoacetanilide is prepared by acetoacetylation of aniline using diketene.{{cite journal |doi=10.15227/orgsyn.021.0004 |title=Acetoacetanilide |journal=Organic Syntheses |date=1941 |volume=21 |page=4|first1=Jonathan W.|last1=Williams|first2=John A.|last2=Krynitsky }} Many analogues have been prepared.{{cite book |doi=10.1002/0471238961.151807011001060605.a01.pub2 |chapter=Pigments, Organic |title=Kirk-Othmer Encyclopedia of Chemical Technology |date=2004 |last1=Jaffe |first1=Edward E. |isbn=978-0-471-48494-3 }}
To make the dyes, acetoacetanilides are coupled to diazonium salts, "azo coupling".K. Hunger. W. Herbst "Pigments, Organic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012. {{doi|10.1002/14356007.a20_371}}
File:AcetoacetylationWithDiketene.svg tautomer is shown.]]
In the presence of sulfuric acid, acetoacetanilide dehydrates to give 4-methyl-2-quinolone.{{cite journal |doi=10.15227/orgsyn.024.0068 |title=4-Methylcarbostyril |journal=Organic Syntheses |date=1944 |volume=24 |page=68|first1=W. M.|last1=Lauer|first2=C. E.|last2=Kaslow }}
Related compounds
- Acetoacetamide, {{chem2|CH3COCH2CONH2}}
- C10H11NO2