Diethyl Malonate → HCID 53942467, compound

HRID 862573Notes

Reaction equation

HRID 862573 reaction equation
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[N+:14]([C:17]1[CH:22]=[CH:21][C:20]([CH2:23][N:24]2[C:28](=[O:29])[C:27]3=[CH:30][CH:31]=[CH:32][CH:33]=[C:26]3[C:25]2=[O:34])=[CH:19][C:18]=1OS(C(F)(F)F)(=O)=O)([O-:16])=[O:15].S([O-])(O)(=O)=O.[K+]>CN(C=O)C>[N+:14]([C:17]1[CH:18]=[CH:19][C:20]([CH2:23][N:24]2[C:28](=[O:29])[C:27]3=[CH:30][CH:31]=[CH:32][CH:33]=[C:26]3[C:25]2=[O:34])=[CH:21][C:22]=1[CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][CH2:12][CH3:13])=[O:10])([O-:16])=[O:15]

Participants

6

Reactant 4

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 516920Potassium bisulfateHCID 19698381HCID 19698381, compound

Product 1

HCID 53942467HCID 53942467, compoundYield 95.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

To a suspension of 60% sodium hydride (5.8 g, 145 mmol) in DMF (150 mL) was added diethyl malonate (26.4 mL, 175 mmol) at room temperature, while the sodium hydride was washed with dry hexane before use. The mixture was heated at 40° C. for 1.5 h, allowed to cool at room temperature and 1-nitro-4-phthalimidomethyl-2-trifluoromethanesulfonyloxybenzene (25 g, 58 mmol) was added. The mixture was stirred overnight at room temperature, poured into 3% potassium hydrogen sulfate, and extracted with a 1:1 toluene/ethyl acetate. The extract was washed successively with 5% potassium hydrogen sulfate, water, saturated aqueous sodium bicarbonate, and brine, dried over magnesium sulfate, and concentrated. The unreacted diethyl malonate was distilled out in vacuo and the residual solid was washed with 1:1 diethyl ether/hexane to give 24.5 g of the title compound.

Workup

  1. washwhile the sodium hydride was washed with dry hexane before use
  2. temperatureto cool at room temperature
  3. extractionextracted with a 1:1 toluene/ethyl acetate
  4. washThe extract was washed successively with 5% potassium hydrogen sulfate, water, saturated aqueous sodium bicarbonate, and brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. distillationThe unreacted diethyl malonate was distilled out in vacuo
  8. washthe residual solid was washed with 1:1 diethyl ether/hexane

Sources & evidence

ORD record
ord-52ee1faa28b3487d956cae14d8e59787
Source dataset
uspto-grants-1998_02
Patent number
US05719152

Reaction notes

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