p-Fluoronitrobenzene → Diethyl methyl(4-nitrophenyl)propanedioate

HRID 573779Notes

Reaction equation

HRID 573779 reaction equation
[H-].[Na+].[CH3:3][CH:4]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:5]([O:7][CH2:8][CH3:9])=[O:6].F[C:16]1[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=1>CS(C)=O>[CH3:3][C:4]([C:16]1[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=1)([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:10]([O:12][CH2:13][CH3:14])=[O:11]

Participants

5

Reactant 3

HCID 9590p-FluoronitrobenzeneHCID 11857Diethyl methylmalonateHCID 24758Sodium hydride

Product 1

HCID 12380744Diethyl methyl(4-nitrophenyl)propanedioate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent3×

Procedure

1.7 g sodium hydride (60% in mineral oil) are suspended in 10 ml dimethylsulfoxide at 0° C. The a solution of 6.4 ml diethyl 2-methylmalonate in 10 ml dimethylsulfoxide is added dropwise. The mixture is stirred for 30 minutes and then diluted with 20 ml dimethylsulfoxide. After stirring for further 2 hours a solution of 5 g 4-fluoronitrobenzene is added dropwise. The mixture is stirred for 12 hours while warming to room temperature. Then it is partitioned between icewater and ethylacetate. The aqueous phase is twice extracted with ethylacetate and the combined organic phases are washed with brine. After drying with magnesium sulphate the solvents are evaporated in vacuo. The residue is chromatographed on silica gel (cyclohexane/ethylacetate 90:10 to 50:50).

Workup

  1. additionis added dropwise
  2. stirringThe mixture is stirred for 12 hours
  3. customThen it is partitioned between icewater and ethylacetate
  4. extractionThe aqueous phase is twice extracted with ethylacetate
  5. washthe combined organic phases are washed with brine
  6. dry with materialAfter drying with magnesium sulphate the solvents
  7. customare evaporated in vacuo
  8. customThe residue is chromatographed on silica gel (cyclohexane/ethylacetate 90:10 to 50:50)

Sources & evidence

ORD record
ord-97919e9776b14c4882a2851d200d2e75
Source dataset
uspto-grants-2015_05
Patent number
US09029544B2

Reaction notes

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