Aminolysis of β-Ketoester. Part I
SyntheticPage 498
DOI:
Submitted: July 29, 2011, published: July 29, 2011
Authors
Sirin Gülten (siringulten@hotmail.com)
A contribution from
Chemicals
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 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.
Keywords
addition, amides, aromatics/arenes, Bisacetoacetamide, ketones, nucleophilic, thermal