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Aminolysis of β-Ketoester I; 3-Oxo-N-[4-[4-(3-oxobutanoylamino)phenyl]ethylphenyl]butanamide

SyntheticPage 498
DOI: 10.1039/SP498
Submitted Jul 29, 2011, published Jul 29, 2011
Sirin Gülten (siringulten@hotmail.com)
A contribution from Gülten Group, Çanakkale


			Reaction Scheme: <img src="/images/empty.gif" alt="" />Aminolysis of &beta;-Ketoester<img src="/images/empty.gif" alt="" /> I

Chemicals Used

4,4´-Diaminodibenzyl (Fluka)
tert-Butyl acetoacetate (Acros Organics)
DMAP (Merck)

Procedure

A mixture of 4,4´-diaminobibenzyl (1.0 g, 4.71 mmol), tert-butyl acetoacetate (1.54 mL, 9.42 mmol) and DMAP (345 mg, 2.82 mmol) in toluene (20 mL) was refluxed overnight. The reaction mixture was cooled to room temperature, the precipitated product was collected by filtration and washed with cold diethyl ether (3x5 mL) and dried. The title compound was obtained as a pale brown solid (1.50 g, 84% yield).

Author's Comments

Aromatic bisacetoacetamides are useful as intermediates in the production of bisacetoacetanilide azo dyes, pigments and polymeric colorants.
This reaction was carried out by Elif Özdemir in the  final year research project under my supervision.

Data

IR-ATR:  3290, 3124, 2937, 2912, 2849, 1713, 1659, 1598, 1529, 1408, 1360, 1339, 1309, 1158, 836 cm-1.
1H NMR (400 MHz, DMSO-d6): ppm = 2.2 (s, 6H, CH3), 2.8 (s, 4H, CH2), 3.53 (s, 4H, CH2), 7.14 (d, 4H, J= 8.4 Hz, CHAr), 7.47 (d, 4H, J= 8.4 Hz, CHAr), 9.99 (s, 2H, NH).
13C NMR (100 MHz, DMSO-d6): ppm = 202.89, 164.74, 136.71, 136.48, 128.60, 118.99, 52.27, 36.51, 30.15.


Lead Reference

Janine Cossy, Annie Thellend, A 4-Dimethylaminopyridine-Catalyzed Aminolysis of β-Ketoesters. Formation of β-Ketoamides, Synthesis, 1989, 753-755.

Other References

Jusong Xia, John W. Miley, Aromatic Bis-Acetoacetamide Intermediates, U.S. Patent, 6500935 B2, 2002.

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Get structure file (.cdx, .sk2, .mol)

Keywords: addition, amides, aromatics/arenes, Bisacetoacetamide, ketones, nucleophilic, thermal

Post new comment
  • Guest chem_boyMay 29 2013 4:12AM

    Did you try this reaction without DMAP?

    • Guest Şirin GültenJun 7 2013 11:51AMRespond to the comment

      The reaction is going with catalyst and without catalyst. I prefer to use DMAP because of better reaction yield and shorter reaction time.

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