Sodium hydride → HCID 67406367, compound

HRID 1372571Notes

Reaction equation

HRID 1372571 reaction equation
[CH2:1]([O:8][C:9]1[C:14]([N+:15]([O-:17])=[O:16])=[CH:13][CH:12]=[C:11](F)[C:10]=1[F:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:20]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])(=[O:29])[CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23].[H-].[Na+]>C1COCC1>[CH2:1]([O:8][C:9]1[C:10]([F:19])=[C:11]([CH:21]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:20]([O:30][C:31]([CH3:34])([CH3:32])[CH3:33])=[O:29])[CH:12]=[CH:13][C:14]=1[N+:15]([O-:17])=[O:16])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 24758Sodium hydride2×HCID 68324Di-tert-butyl malonate2×HCID 178588811-Benzyloxy-2,3-difluoro-6-nitrobenzene

Product 1

HCID 67406367HCID 67406367, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

In THF (100 ml) were dissolved 1-benzyloxy-2,3-difluoro-6-nitrobenzene (4.17 g, 15.7 mmol) and di-tert-butyl malonate (3.52 ml, 15.7 mmol). To the resulting solution was added sodium hydride (60% in oil, 1.26 g, 31.4 mmol) in portions under stirring at 0° C. The reaction mixture was stirred at 0° C. for 30 minutes and then at 80° C. for 9 hours. Di-tert-butyl malonate (7.04 ml, 31.4 mmol) and sodium hydride (60%; 2.52 g, 52.8 mmol) were added and the mixture was stirred at 80° C. for 2 days. After cooling to room temperature, the reaction mixture was poured in ice water (100 ml), followed by extraction with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate and distilled under reduced pressure to remove the solvent. The residue was purified by chromatography on a silica gel column (silica gel: 200 g), whereby from hexane/ethyl acetate (8/1) eluate fractions, the title compound (6.87 g, 95%) was obtained as an orange solid.

Workup

  1. stirringThe reaction mixture was stirred at 0° C. for 30 minutes
  2. stirringthe mixture was stirred at 80° C. for 2 days
  3. temperatureAfter cooling to room temperature
  4. extractionfollowed by extraction with ethyl acetate
  5. washThe extract was washed with saturated brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. distillationdistilled under reduced pressure
  8. customto remove the solvent
  9. customThe residue was purified by chromatography on a silica gel column (silica gel: 200 g), whereby from hexane/ethyl acetate (8/1) eluate fractions

Sources & evidence

ORD record
ord-7382b9ba0194474fa0ba36968a85abfa
Source dataset
uspto-grants-2007_01
Patent number
US07157487B2

Reaction notes

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