Lithium Chloride → (5-Methyl-3-nitro-pyridin-2-yl)-acetic acid ethyl ester

HRID 1838303Notes

Reaction equation

HRID 1838303 reaction equation
[Li+].[Cl-].[CH2:3]([O:5][C:6](=[O:23])[CH:7]([C:13]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][C:16]([CH3:22])=[CH:15][N:14]=1)C(OCC)=O)[CH3:4]>CS(C)=O.O>[CH2:3]([O:5][C:6](=[O:23])[CH2:7][C:13]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][C:16]([CH3:22])=[CH:15][N:14]=1)[CH3:4]

Participants

5

Reactant 2

HCID 433294Lithium ChlorideHCID 600601582-(5-Methyl-3-nitro-pyridin-2-yl)-malonic acid diethyl ester

Product 1

HCID 60060147(5-Methyl-3-nitro-pyridin-2-yl)-acetic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Conditions

Temperature
150 °C

Procedure

LiCl (10.6 g, 0.252 mol) is suspended in a solution of 2-(5-Methyl -3-nitro-pyridin-2-yl)-malonic acid diethyl ester (50 g, 0.168 mol) in DMSO (100 mL) containing water (12 g, 0.678 mol) and is stirred at 150° C. for 3 h. The reaction mixture is cooled, diluted with water (200 mL), and extracted with ethyl acetate. The combined organic phase are washed successively with saturated aqueous NaHCO3, water, brine, dried over Na2SO4, and concentrated in vacuo. The residue is purified by silica gel chromatography eluting with 20% EtOAc-hexanes to afford (5-Methyl-3-nitro-pyridin-2-yl)-acetic acid ethyl ester as an oil; 1H NMR (300 MHz, CDCl3) δ 1.23 (t, J=9 Hz, 3H), 4.15 (q, J=9 Hz, 2H), 4.25 (s, 2H), 8.2 (s, 1H), 8.58 (s, 1H).

Workup

  1. temperatureThe reaction mixture is cooled
  2. extractionextracted with ethyl acetate
  3. washThe combined organic phase are washed successively with saturated aqueous NaHCO3, water, brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe residue is purified by silica gel chromatography
  7. washeluting with 20% EtOAc-hexanes

Sources & evidence

ORD record
ord-7aaec556f29d46da9c4bd87a088d67e1
Source dataset
uspto-grants-2004_01
Patent number
US06673811B1

Reaction notes

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