Diethyl Malonate → Diethyl 2-(2,3-difluoro-4-nitrophenyl)malonate

HRID 2061479Notes

Reaction equation

HRID 2061479 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].[F:14][C:15]1[C:20]([F:21])=[C:19](F)[CH:18]=[CH:17][C:16]=1[N+:23]([O-:25])=[O:24].[Cl-].[NH4+].FC1C(F)=CC=C([N+]([O-])=O)C=1C(C(OCC)=O)C(OCC)=O>CN1CCCC1=O>[F:21][C:20]1[C:15]([F:14])=[C:16]([N+:23]([O-:25])=[O:24])[CH:17]=[CH:18][C:19]=1[CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8]

Participants

7

Reactant 5

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 698711,2,3-Trifluoro-4-nitrobenzeneHCID 68625680Diethyl 2-(2,3-difluoro-6-nitrophenyl)malonate

Product 1

HCID 59683248Diethyl 2-(2,3-difluoro-4-nitrophenyl)malonate

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent2×

Procedure

To diethyl malonate (5.1 g, 32 mmol) in N-methylpyrrolidone (50 ml) at 0° C. were added sodium hydride (1.6 g×60% in oil) then 2,3,4-trifluoronitrobenzene (5.4 g, 31 mmol) in more N-methylpyrrolidone (10 ml) at 20° C. After 2 h at room temperature the reaction was poured into aqueous ammonium chloride and extracted with ethyl acetate. Drying (MgSO4), evaporation, and chromatography of a 10% sample of the product (20 g silica with 0-25% ethyl acetate in hexane) gave 0.5 g of a 1:1 mixture of the title compound and diethyl 2-(2,3-difluoro-6-nitrophenyl)malonate which was used directly in D16.

Workup

  1. customat 20° C
  2. extractionextracted with ethyl acetate
  3. customDrying
  4. custom(MgSO4), evaporation, and chromatography of a 10% sample of the product (20 g silica with 0-25% ethyl acetate in hexane)
  5. customgave

Sources & evidence

ORD record
ord-4ef11edcf9b144f18157621c3d25b3f3
Source dataset
uspto-grants-2012_10
Patent number
US08283364B2

Reaction notes

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