Dimethyl malonate → Dimethyl 2-(2-fluoro-4-nitrophenyl)malonate

HRID 1842952Notes

Reaction equation

HRID 1842952 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].C([O-])([O-])=O.[K+].[K+].F[C:17]1[CH:22]=[CH:21][C:20]([N+:23]([O-:25])=[O:24])=[CH:19][C:18]=1[F:26]>CN(C=O)C>[F:26][C:18]1[CH:19]=[C:20]([N+:23]([O-:25])=[O:24])[CH:21]=[CH:22][C:17]=1[CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 11430Potassium CarbonateHCID 1230531,2-Difluoro-4-nitrobenzene

Product 1

HCID 53429620Dimethyl 2-(2-fluoro-4-nitrophenyl)malonateYield 76.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

To a stirred solution of dimethyl malonate (6.22 g, 47.1 mmol, 1.5 eq) in DMF (30 mL) was added K2CO3 (8.70 g, 63 mmol, 2.0 eq) and heated to 50° C. for 30 min when 1,2-difluoro-4-nitrobenzene (5.0 g, 31.4 mmol, 1.0 eq) was added and the reaction mixture was stirred for 5 h at 50° C. The reaction mixture was cooled to RT, filtered to remove K2CO3, and the DMF was evaporated under vacuum. The residue was diluted with EtOAc (100 mL), washed with water, brine, dried over Na2SO4 and evaporated to get dimethyl 2-(2-fluoro-4-nitrophenyl)malonate (6.5 g, 76%) as a solid (TLC system: EtOAc/PE (3:7), Rf: 0.50).

Workup

  1. additionwas added
  2. temperatureThe reaction mixture was cooled to RT
  3. filtrationfiltered
  4. customto remove K2CO3
  5. customthe DMF was evaporated under vacuum
  6. additionThe residue was diluted with EtOAc (100 mL)
  7. washwashed with water, brine
  8. dry with materialdried over Na2SO4
  9. customevaporated

Sources & evidence

ORD record
ord-b36578ecb6a542c0bfd593989ee1cb60
Source dataset
uspto-grants-2015_02
Patent number
US08946204B2

Reaction notes

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