Sodium hydride → tert-Butyl ethyl (5-nitropyridin-2-yl)malonate

HRID 2173321Notes

Reaction equation

HRID 2173321 reaction equation
[H-].[Na+].[C:3]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Cl[C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][N:18]=1>CN(C=O)C>[N+:23]([C:20]1[CH:21]=[CH:22][C:17]([CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][C:12]([CH3:14])([CH3:13])[CH3:15])=[O:10])=[N:18][CH:19]=1)([O-:25])=[O:24]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 783082-Chloro-5-nitropyridineHCID 96345tert-Butyl ethyl malonate

Product 1

HCID 54383765tert-Butyl ethyl (5-nitropyridin-2-yl)malonate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a suspension of NaH (60% in oil, 1.89 g, 47 mmol) in 20 mL of DMF was added tert-butyl ethyl propanedioate (6.5 g, 34.7 mmol) at room temperature. The mixture was stirred for 30 min. A solution of 2-chloro-5-nitropyridine (5.0 g, 31.5 mmol) in 10 mL of DMF was added. The mixture was stirred at r.t. overnight. The solvent was removed under reduce pressure. Water was added and the mixture was extracted with EtOAc. The combined organic layer was washed with brine, dried over anhydrous Na2SO4, concentrated and the residue was purified by column chromatography with silca gel to give tert-butyl ethyl (5-nitropyridin-2-yl)propanedioate. 1H-NMR (400 MHz, CDCl3) δ 9.39 (s, 1H), 8.51 (d, J=8.8 Hz, 1H), 7.76 (d, J=8.8 Hz, 1H), 5.00 (s, 1H), 4.28 (q, J=7.2 Hz, 2H), 1.49 (s, 9H), 1.31 (t, J=7.2 Hz, 3H).

Workup

  1. stirringThe mixture was stirred at r.t. overnight
  2. customThe solvent was removed
  3. additionWater was added
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated
  8. customthe residue was purified by column chromatography with silca gel

Sources & evidence

ORD record
ord-5098ffdd206f4a5a89ad99c2f7d443e7
Source dataset
uspto-grants-2015_06
Patent number
US09056859B2

Reaction notes

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