Chemistry:Acetoacetanilide

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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.[1] For the general case of substituted acetoanilides, substituents on the aryl ring affect the balance of intra- vs intermolecular hydrogen bonding.[2] The situation is illustrated by the 2' vs. 3' vs. 4' fluoro-substituted acetoacetanilides.[3]

Preparation and reactions

Acetoacetanilide is prepared by acetoacetylation of aniline using diketene.[4] Many analogues have been prepared.[5]

To make the dyes, acetoacetanilides are coupled to diazonium salts, "azo coupling".[6]

Acetoacetylation with diketene followed by diazo coupling. The ketohydrazone tautomer is shown.

In the presence of sulfuric acid, acetoacetanilide dehydrates to give 4-methyl-2-quinolone.[7]

References

  1. ↑ Gilli, Paola; Bertolasi, Valerio; Ferretti, Valeria; Gilli, Gastone (2000). "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 of the American Chemical Society 122 (42): 10405. doi:10.1021/ja000921+. Bibcode: 2000JAChS.12210405G. 
  2. ↑ Kubozono, Yoshihiro; Kohno, Isao; Ooishi, Kazuo; Namazue, Sakuhiro; Haisa, Masao; Kashino, Setsuo (1992). "Crystal and Molecular Structures of Acetoacetanilide, and o - and p -Chloroacetoacetanilides: X-Ray Crystallographic and MO Study". Bulletin of the Chemical Society of Japan 65 (12): 3234–3240. doi:10.1246/bcsj.65.3234. 
  3. ↑ Chisholm, Greig; Kennedy, Alan R.; Beaton, Laura; Brook, Eve (2002). "Structural motifs in acetoacetanilides: The effect of a fluorine substituent". Acta Crystallographica Section C Crystal Structure Communications 58 (11): o645–o648. doi:10.1107/S0108270102016086. PMID 12415169. Bibcode: 2002AcCrC..58O.645C. 
  4. ↑ Williams, Jonathan W.; Krynitsky, John A. (1941). "Acetoacetanilide". Organic Syntheses 21: 4. doi:10.15227/orgsyn.021.0004. 
  5. ↑ Jaffe, Edward E. (2004). "Pigments, Organic". Kirk-Othmer Encyclopedia of Chemical Technology. doi:10.1002/0471238961.151807011001060605.a01.pub2. ISBN 978-0-471-48494-3. 
  6. ↑ K. Hunger. W. Herbst "Pigments, Organic" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012. doi:10.1002/14356007.a20_371
  7. ↑ Lauer, W. M.; Kaslow, C. E. (1944). "4-Methylcarbostyril". Organic Syntheses 24: 68. doi:10.15227/orgsyn.024.0068. 



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