Dimethyl malonate → Dimethyl 2-methoxycarbonyl-6-nitrophenylmalonate

HRID 1008144Notes

Reaction equation

HRID 1008144 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 an ice-cold suspension of 2.1 g sodium hydride in 15 mL DMSO. The reaction mixture was stirred at 100° C. for 1 hour and then cooled to room temperature. 2-Chloro-3-methoxycarbonylnitrobenzene (2.15 g) was added in one portion and the mixture was heated to 100° C. for 1.5 hours. The reaction mixture was then cooled to room temperature, poured into ice water, acidified to pH 5 and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate and concentrated to give 3.0 g of the dimethyl 2-methoxycarbonyl-6-nitrophenyl-malonate.

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 washed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-d53dbad16c154cb2b00f6b82e4d31ffb
Source dataset
uspto-grants-2004_09
Patent number
US06797725B2

Reaction notes

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