Diethyl Oxalate → Ethyl 3-(3-nitropyridin-2-yl)-2-oxopropionate

HRID 1693368Notes

Reaction equation

HRID 1693368 reaction equation
[O-]CC.[K+].[C:5]([O:12][CH2:13][CH3:14])(=[O:11])[C:6]([O:8]CC)=O.[CH3:15][C:16]1[C:21]([N+:22]([O-:24])=[O:23])=[CH:20][CH:19]=[CH:18][N:17]=1>C(OCC)C.C(O)C>[CH2:13]([O:12][C:5](=[O:11])[C:6](=[O:8])[CH2:15][C:16]1[C:21]([N+:22]([O-:24])=[O:23])=[CH:20][CH:19]=[CH:18][N:17]=1)[CH3:14]

Participants

6

Reactant 3

HCID 7268Diethyl OxalateHCID 3293602-Methyl-3-nitropyridineHCID 23670592Potassium ethoxide

Product 1

HCID 59753617Ethyl 3-(3-nitropyridin-2-yl)-2-oxopropionate

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 3283Diethyl EtherSolvent

Procedure

To a solution of potassium ethoxide (2.44 g, 27.7 mmol) in diethyl ether (90 mL) and ethanol (8 mL) was added diethyl oxalate (3.79 mL, 27.7 mmol) resulting in a yellow suspension. The reaction mixture was stirred for 5 min prior to the addition of 2-methyl-3-nitropyridine (Preparation 29, 3.40 g, 24.6 mmol) in one portion. The resulting red suspension was stirred at rt, under argon, for 20 h. The mixture was filtered, washed thoroughly with diethyl ether and dried. The red solid was dissolved in water and the mixture adjusted to pH 4 by addition of glacial acetic acid. The resulting precipitate was collected by filtration, dissolved in dichloromethane, washed with brine, dried (MgSO4), and then filtered and concentrated in vacuo to give the title compound as an orange solid. δH (CDCl3): 1.40 (3H, t), 4.39 (2H, q), 7.34 (1H, s), 7.36 (1H, dd), 8.43 (1H, dd), 8.66 (1H, dd).

Workup

  1. customresulting in a yellow suspension
  2. stirringThe resulting red suspension was stirred at rt, under argon, for 20 h
  3. filtrationThe mixture was filtered
  4. washwashed thoroughly with diethyl ether
  5. customdried
  6. dissolutionThe red solid was dissolved in water
  7. additionthe mixture adjusted to pH 4 by addition of glacial acetic acid
  8. filtrationThe resulting precipitate was collected by filtration
  9. dissolutiondissolved in dichloromethane
  10. washwashed with brine
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-348365cc819f496198e832965a856470
Source dataset
uspto-grants-2012_04
Patent number
US08158622B2

Reaction notes

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