Acetic Acid → Ethyl 2-bromo-5-nitro-α-oxo-4-pyridinepropanoate

HRID 751619

Reaction equation

HRID 751619 reaction equation
[O-]CC.[K+].[C:5]([O:12][CH2:13][CH3:14])(=[O:11])[C:6]([O:8]CC)=O.[Br:15][C:16]1[CH:21]=[C:20]([CH3:22])[C:19]([N+:23]([O-:25])=[O:24])=[CH:18][N:17]=1.C(O)(=O)C>C(OCC)C.C(O)C.O>[CH2:13]([O:12][C:5](=[O:11])[C:6](=[O:8])[CH2:22][C:20]1[C:19]([N+:23]([O-:25])=[O:24])=[CH:18][N:17]=[C:16]([Br:15])[CH:21]=1)[CH3:14]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 7268Diethyl OxalateHCID 3458732-Bromo-4-methyl-5-nitropyridineHCID 23670592Potassium ethoxide

Product 1

HCID 59753623Ethyl 2-bromo-5-nitro-α-oxo-4-pyridinepropanoate

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of potassium ethoxide (2.05 g, 24.3 mmol) in diethyl ether (70 mL) and ethanol (10 mL) under an argon atmosphere was added diethyl oxalate (3.3 mL, 24.3 mmol) and the reaction stirred at rt for 15 min. A solution of 2-bromo-4-methyl-5-nitropyridine (Preparation 24, 4.8 g, 22.1 mmol) in diethyl ether (20 mL) was added to the reaction mixture giving an immediate black precipitate. The reaction was allowed to stir at rt for 6 h, then cooled to 0° C. and filtered to give a black solid. The solid was dissolved in water (250 mL) and acidified to pH 4 with acetic acid resulting in formation of a red precipitate. The solid was collected and dried to give the title compound as a red solid. δH (d6 DMSO): 1.16 (3H, t), 4.01 (2H, q), 6.55 (1H, s), 7.92 (1H, s), 8.96 (1H, s).

Workup

  1. customgiving an immediate black precipitate
  2. stirringto stir at rt for 6 h
  3. temperaturecooled to 0° C.
  4. filtrationfiltered
  5. customto give a black solid
  6. customThe solid was collected
  7. customdried

Sources & evidence

ORD record
ord-012a2cae1fe2468fa90312d42541e3d5
Source dataset
uspto-grants-2008_07
Patent number
US07405210B2

Linked notes

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