Dimethyl malonate → Dimethyl-3-nitrobiphenyl-4-malonate

HRID 1019133Notes

Reaction equation

HRID 1019133 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[H-].[Na+].F[C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:15][C:14]=1[N+:25]([O-:27])=[O:26]>CS(C)=O>[CH3:6][O:5][C:3](=[O:4])[CH:2]([C:13]1[CH:18]=[CH:17][C:16]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[CH:15][C:14]=1[N+:25]([O-:27])=[O:26])[C:1]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 106802714-Fluoro-3-nitro-1,1'-biphenyl

Product 1

HCID 10711410Dimethyl-3-nitrobiphenyl-4-malonate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent3×

Conditions

Temperature
100 °C

Procedure

Dimethyl malonate (10 mL) in 25 mL of dimethylsulfoxide was added dropwise to 3.5 g sodium hydride suspended in 25 mL dimethylsulfoxide and the mixture heated at 100° C. for 10 minutes. The mixture was cooled to room temperature and 4.7 g of 4-fluoro-3-nitrobiphenyl in 25 mL dimethylsulfoxide was added. The mixture was heated at 100° C. for 2 hours, cooled and quenched with 300 mL of saturated ammonium chloride solution. The mixture was extracted three times with ethyl acetate and the combined organic layers washed with water and brine and evaporated to give, as a yellow oil, crude dimethyl-3-nitrobiphenyl-4-malonate.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. temperatureThe mixture was heated at 100° C. for 2 hours
  3. temperaturecooled
  4. customquenched with 300 mL of saturated ammonium chloride solution
  5. extractionThe mixture was extracted three times with ethyl acetate
  6. washthe combined organic layers washed with water and brine
  7. customevaporated

Sources & evidence

ORD record
ord-9542f8f437d14732a07e786805b45ef2
Source dataset
uspto-grants-2002_11
Patent number
US06486185B1

Reaction notes

Loading…