Dimethyl malonate → Dimethyl 2-methoxycarbonyl-6-nitrophenylmalonate

HRID 1019157Notes

Reaction equation

HRID 1019157 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[H-].[Na+].Cl[C:13]1[C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][CH:16]=[CH:15][C:14]=1[N+:23]([O-:25])=[O:24]>CS(C)=O>[CH3:22][O:21][C:19]([C:18]1[CH:17]=[CH:16][CH:15]=[C:14]([N+:23]([O-:25])=[O:24])[C:13]=1[CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])=[O:20]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 10751184Methyl 2-chloro-3-nitrobenzoate

Product 1

HCID 54355276Dimethyl 2-methoxycarbonyl-6-nitrophenylmalonate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
100 °C

Procedure

Dimethyl malonate (6.0 mL) was added to the ice-cold suspension of 2.1 g of sodium hydride in 16 mL of DMSO. The reaction mixture was then stirred at 100° C. for 1 hour and cooled to room temperature. 2-chloro-3-methoxycarbonyl-nitrobenzene (2.15 g) was added to the above mixture in one portion and the mixture was heated to 100° C. for 1.5 hours. The reaction mixture was then cooled to room temperature and poured into ice water, acidified to pH of 5, and extracted with ethyl acetate. The organic layer was then washed with brine, dried over anhydrous sodium sulfate and concentrated to give 3.0 g of the dimethyl 2-methoxycarbonyl-6-nitrophenylmalonate.

Workup

  1. temperaturecooled to room temperature
  2. temperaturethe mixture was heated to 100° C. for 1.5 hours
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was then washed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-11d406c8bb1a4eef9229b238ff1e2f1c
Source dataset
uspto-grants-2002_11
Patent number
US06486185B1

Reaction notes

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