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

HRID 602442Notes

Reaction equation

HRID 602442 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.[H-].[Na+].[C:13]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])(=[O:20])[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]>CN(C)C=O>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([CH:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:13]([O:21][C:22]([CH3:25])([CH3:23])[CH3:24])=[O:20])=[N:3][CH:4]=1)([O-:10])=[O:9]

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)malonateYield 82.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred suspension of 2-chloro-5-nitropyridine (7.66 g, 48.3 mmol), sodium hydride (60% in mineral oil, 2.13 g, 53.1 mmol) in N,N-dimethylformamide (100 mL) was added tert-butyl ethyl malonate (10.0 g, 53.1 mmol) dropwise at room temperature, and the mixture was stirred at room temperature for 20 h. The mixture was washed with water (300 mL×5), brine (100 mL), dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was chromatographed on a column of silica gel eluting with n-hexane/ethyl acetate (5:1) to give 12.3 g (82%) of the title compound as a brown oil.

Workup

  1. washThe mixture was washed with water (300 mL×5), brine (100 mL)
  2. dry with materialdried over magnesium sulfate
  3. concentrationconcentrated under reduced pressure
  4. customThe resulting residue was chromatographed on a column of silica gel eluting with n-hexane/ethyl acetate (5:1)

Sources & evidence

ORD record
ord-a2de72df05664146bd44f06f57ca2623
Source dataset
uspto-grants-2011_03
Patent number
US07906532B2

Reaction notes

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