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Aminolysis of β-Ketoester. Part II; 3-Oxo-N-[4-[4-(-3oxobutanoylamino) phenoxy]phenyl]butanamide

SyntheticPage 499
DOI: 10.1039/SP499
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. Part II<img src="/images/empty.gif" alt="" />

Chemicals Used

4,4´-Diaminodiphenyl ether (Merck)
tert-Butyl acetoacetate (Acros Organics)
DMAP (Merck)

Procedure

A mixture of 4,4´-diaminodiphenyl ether (1.0 g, 4.99 mmol), tert-butyl acetoacetate (1.63 mL, 9.98 mmol) and DMAP (364 mg, 2.99 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 cream coloured solid (1.71 g, 93% 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 Nilüfer Hamarat in the  final year research project under my supervision.

Data

IR-ATR:  3279, 3254, 3140, 3071, 2920, 1713, 1651, 1611, 1534, 1497, 1221, 1162, 838 cm-1.
1H NMR (400 MHz, DMSO-d6): ppm = 2.21 (s, 6H, CH3), 3.54 (s, 4H, CH2), 6.96 (d, 4H, J= 8.86 Hz, CHAr), 6.96 (d, 4H, J=8.86 Hz, CHAr), 10.08 (s, 2H, NH).
13C NMR (100 MHz, DMSO-d6): ppm = 203.3, 165.26, 153.09, 134.91, 121.24, 119.3, 52.72, 30.62.


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

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