1-Chloro-4-nitrobenzene → Diethyl 2-ethyl-2-(4-nitrophenyl)malonate

HRID 1904017

Reaction equation

HRID 1904017 reaction equation
[H-].[Na+].[CH2:3]([CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:4].[H][H].Cl[C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=1>CN(C)C=O>[CH2:3]([C:5]([C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][CH:20]=1)([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:4]

Participants

6

Reactant 4

HCID 74741-Chloro-4-nitrobenzeneHCID 8610Diethyl ethylmalonateHCID 24758Sodium hydrideHCID 178418361HCID 178418361, compound

Product 1

HCID 20465989Diethyl 2-ethyl-2-(4-nitrophenyl)malonateYield 79%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
100 °C

Procedure

In 100 ml of N,N-dimethylformamide was suspended 11 g of 50% sodium hydride which had been washed with n-hexane and the suspension was stirred under ice cooling. Thereafter, 37.6 g (0.2 mole) of diethyl ethylmalonate was added dropwise thereto and stirring was continued until evolution of hydrogen ceased. Subsequently, a solution of 31.51 g (0.2 mole) of p-chloronitrobenzene in 50 ml of N,N-dimethylformamide was added dropwise. At the end of the dropwise addition, the mixture was heated on an oil bath at 100° C. for 9 hours and N,N-dimethylformamide was distilled off in vacuo. The residue was extracted with ethyl acetate and the ethyl acetate layer was washed with 5% hydrochloric acid and saturated sodium chloride solution and then dried over magnesium sulfate. The ethyl acetate was distilled off in vacuo and the residue was subjected to chromatography on silica gel eluting with a mixture of benzene and n-hexane (1:1) to give 48.64 g (0.157 mole, 79% yield) of diethyl 2-ethyl-2-(4-nitrophenyl)malonate.

Workup

  1. washhad been washed with n-hexane
  2. stirringstirring
  3. additionAt the end of the dropwise addition
  4. distillationN,N-dimethylformamide was distilled off in vacuo
  5. extractionThe residue was extracted with ethyl acetate
  6. washthe ethyl acetate layer was washed with 5% hydrochloric acid and saturated sodium chloride solution
  7. dry with materialdried over magnesium sulfate
  8. distillationThe ethyl acetate was distilled off in vacuo
  9. additionthe residue was subjected to chromatography on silica gel eluting with a mixture of benzene and n-hexane (1:1)

Sources & evidence

ORD record
ord-636d4b9d2a7d4b3caa872ee05cc53f2c
Source dataset
uspto-grants-1984_03
Patent number
US04439448

Linked notes

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