Methyl acetoacetate → HCID 24810447, compound

HRID 1919584Notes

Reaction equation

HRID 1919584 reaction equation
[C:1](O)(=O)C.[F:5][C:6]1[CH:14]=[C:13]([F:15])[CH:12]=[C:11]([F:16])[C:7]=1[C:8]([NH2:10])=[NH:9].[Cl:17][C:18]1[CH:25]=[C:24]([F:26])[CH:23]=[CH:22][C:19]=1[CH:20]=O.[C:27]([O:33][CH3:34])(=[O:32])[CH2:28][C:29]([CH3:31])=O.C([O-])(=O)C.[Na+]>C(O)C>[F:5][C:6]1[CH:14]=[C:13]([F:15])[CH:12]=[C:11]([F:16])[C:7]=1[C:8]1[NH:10][C:29]([CH3:31])=[C:28]([C:27]([O:33][CH2:34][CH3:1])=[O:32])[CH:20]([C:19]2[CH:22]=[CH:23][C:24]([F:26])=[CH:25][C:18]=2[Cl:17])[N:9]=1

Participants

6

Reactant 4

HCID 7757Methyl acetoacetateHCID 1450242-Chloro-4-fluorobenzaldehydeHCID 517045Sodium AcetateHCID 67234591HCID 67234591, compound

Product 1

HCID 24810447HCID 24810447, compoundYield 34%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

2 mmol 2,4,6-Trifluorobenzamidine acetate (Judkins, B. D., Allen, D. G., Cook, T. A. Synth. Commun. 1996, 26(23):4351-4367), 2 mmol 2-chloro-4-fluorobenzaldehyde, 2 mmol methyl acetoacetate and 2.2 mmol sodium acetate were reacted under reflux in 10 ml anhydrous ethanol for 20 hr, concentrated, and then ethyl acetate and water were added to separate the layers. The ethyl acetate layer was dried over anhydrous sodium sulfate, and separated by a column chromatography to obtain 0.29 g of a colorless fine needle crystal with mp 184-186° C.; 1H-NMR (400 MHz, DMSO-d6) δ 1.02-1.05 (3H, t, J=7.3 Hz); 2.32 (3H, s); 3.92-3.95 (2H, m, J=7.3 Hz); 5.97 (1H, s); 7.21-7.45 (5H, m); MS (EI) 426 (M+).

Workup

  1. concentrationconcentrated
  2. additionethyl acetate and water were added
  3. customto separate the layers
  4. dry with materialThe ethyl acetate layer was dried over anhydrous sodium sulfate
  5. customseparated by a column chromatography

Sources & evidence

ORD record
ord-9bc038cd1e2c432a8f2f4aeb3faa69a4
Source dataset
uspto-grants-2012_05
Patent number
US08168642B2

Reaction notes

Loading…