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

HRID 1502106Notes

Reaction equation

HRID 1502106 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 silica 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 silica gel

Sources & evidence

ORD record
ord-372550a22d084bc58989f720c3bf88ed
Source dataset
uspto-grants-2015_12
Patent number
US09206199B2

Reaction notes

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