Diethyl methylmalonate → Diethyl 2-(2-bromo-4-nitrophenyl)-2-methylmalonate

HRID 1665769Notes

Reaction equation

HRID 1665769 reaction equation
[CH3:1][CH:2]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].[Br:15][C:16]1[CH:21]=[C:20]([N+:22]([O-:24])=[O:23])[CH:19]=[CH:18][C:17]=1F>CN(C=O)C>[Br:15][C:16]1[CH:21]=[C:20]([N+:22]([O-:24])=[O:23])[CH:19]=[CH:18][C:17]=1[C:2]([CH3:1])([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

5

Reactant 3

HCID 11857Diethyl methylmalonateHCID 24758Sodium hydrideHCID 696992-Bromo-1-fluoro-4-nitrobenzene

Product 1

HCID 59206132Diethyl 2-(2-bromo-4-nitrophenyl)-2-methylmalonateYield 99%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

Diethyl 2-methylmalonate (4.31 mL, 25.0 mmol) was dissolved in 25 mL of anhydrous DMF. This solution was cooled to 0° C. under an atmosphere of nitrogen. Sodium hydride (1.04 g, 26 mmol, 60% by weight in mineral oil) was slowly added to the solution. The resulting mixture was allowed to stir for 3 minutes at 0° C., and then at room temperature for 10 minutes. 2-Bromo-1-fluoro-4-nitrobenzene (5.00 g, 22.7 mmol) was quickly added and the mixture turned bright red. After stirring for 10 minutes at room temperature, the crude mixture was evaporated to dryness and then partitioned between dichloromethane and a saturated aqueous solution of sodium chloride. The layers were separated and the organic phase was washed twice with a saturated aqueous solution of sodium chloride. The organics were concentrated to yield diethyl 2-(2-bromo-4-nitrophenyl)-2-methylmalonate (8.4 g, 99%) as a pale yellow oil which was used without further purification. Retention time 1.86 min.

Workup

  1. waitat room temperature for 10 minutes
  2. stirringAfter stirring for 10 minutes at room temperature
  3. customthe crude mixture was evaporated to dryness
  4. custompartitioned between dichloromethane
  5. customThe layers were separated
  6. washthe organic phase was washed twice with a saturated aqueous solution of sodium chloride
  7. concentrationThe organics were concentrated

Sources & evidence

ORD record
ord-0dfa10188f174486b585cd780ae9f48c
Source dataset
uspto-grants-2011_10
Patent number
US08039491B2

Reaction notes

Loading…