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

HRID 1842968Notes

Reaction equation

HRID 1842968 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][CH:18]=1>CN(C=O)C.O>[N+:23]([C:20]1[CH:21]=[CH:22][C:17]([CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])=[CH:18][CH:19]=1)([O-:25])=[O:24]

Participants

6

Reactant 3

HCID 7943Dimethyl malonateHCID 9590p-FluoronitrobenzeneHCID 11430Potassium Carbonate

Product 1

HCID 2764303Dimethyl 2-(4-nitrophenyl)malonateYield 78%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

To a suspension of dimethyl malonate (9.77 mL, 85.07 mmol, 1.2 eq) in DMF (100 mL) and K2CO3 (29.36 g, 212.76 mmol, 3.0 eq) was added 1-fluoro-4-nitrobenzene (7.51 mL, 70.91 mmol, 1.0 eq) at RT and the mixture was stirred for 16 h at 70° C. The reaction mixture was cooled to RT and diluted with water (200 mL) and extracted with ethyl acetate (2×100 mL). The ethyl acetate layers were collected, washed with cold water (2×50 mL), brine (50 mL), dried over sodium sulfate and evaporated under vacuum. The crude product was washed with n-pentane (50 mL) to get dimethyl 2-(4-nitrophenyl)malonate 14 g, 78%) as pale yellow solid (TLC system: EtOAc/PE (3:7), Rf: 0.50).

Workup

  1. temperatureThe reaction mixture was cooled to RT
  2. extractionextracted with ethyl acetate (2×100 mL)
  3. customThe ethyl acetate layers were collected
  4. washwashed with cold water (2×50 mL), brine (50 mL)
  5. dry with materialdried over sodium sulfate
  6. customevaporated under vacuum
  7. washThe crude product was washed with n-pentane (50 mL)

Sources & evidence

ORD record
ord-6d6433e6166749f9a68187d1bae10c46
Source dataset
uspto-grants-2015_02
Patent number
US08946204B2

Reaction notes

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