Water → HCID 66896443, compound

HRID 1394580Notes

Reaction equation

HRID 1394580 reaction equation
[H-].[Na+].[CH3:3][CH2:4][O:5][C:6]([CH:8](P(OCC)(OCC)=O)[F:9])=[O:7].[C:18]([C:21]1[O:25][C:24]2[C:26]([C:30]3[CH:35]=[C:34]([CH2:36][CH3:37])[CH:33]=[C:32]([C:38]([CH3:41])([CH3:40])[CH3:39])[C:31]=3[O:42][CH2:43][CH2:44][CH3:45])=[CH:27][CH:28]=[CH:29][C:23]=2[CH:22]=1)(=O)[CH3:19].O>CN(C=O)C>[CH2:4]([O:5][C:6](=[O:7])[C:8]([F:9])=[C:18]([C:21]1[O:25][C:24]2[C:26]([C:30]3[CH:35]=[C:34]([CH2:36][CH3:37])[CH:33]=[C:32]([C:38]([CH3:41])([CH3:40])[CH3:39])[C:31]=3[O:42][CH2:43][CH2:44][CH3:45])=[CH:27][CH:28]=[CH:29][C:23]=2[CH:22]=1)[CH3:19])[CH3:3]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 2734865Triethyl 2-fluoro-2-phosphonoacetateHCID 59682056HCID 59682056, compound

Product 1

HCID 66896443HCID 66896443, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a mixture of 43 mg (0.89 mmol) of NaH in 1 mL of dry DMF was added 216 mg (0.89 mmol, 0.15 mL) of triethyl 2-fluoro-2-phosphonoacetate diluted in 1 mL of dry DMP at 0° C. After the gas evolution ceased, the solution was stirred at this temperature for 15 minutes and 0.296 mmol of 2-acetyl-7-(2-propoxy-3-tert-butyl-5-ethylphenyl) benzo[b]furan diluted in 1 mL of dry DMF was added dropwise. The reddish solution was stirred to 0° C. until completion (TLC monitoring). After cooling, water was added and the mixture as extracted with ethyl acetate. The organic layer was washed with water and brine and dried over MgSO4. The solvents were evaporated under reduced pressure, and the residual oil was purified over silica gel (eluent: ethyl acetate/hexane: 5/95) to afford 2-fluoro-3-[7-(2-propoxy-3-tert-butyl-5-ethylphenyl)-benzo[b]furan-2-yl]-but-2-enoic acid ethyl ester as a clear yellow oil. 1H NMR (CDCl3), δ: 7.52 (d, J=7.8 Hz, 1H), 7.52 (d, J=7.2 Hz, 1H), 7.39 (d, J=3.4 Hz, 1H), 7.33 (t, J=7.6 Hz, 1H), 7.22 (d, J=2.1 Hz, 1H), 7.17 (d, J=2.2 Hz, 1H), 3.27 (t, J=6.2 Hz, 2H), 2.66 (dd, J=15.1, 7.5 Hz, 1H), 2.54 (d, J=3.4 Hz, 3H), 1.46 (s, 9H), 1.27 (t, J=7.7 Hz, 3H), 1.19 (m, 2H), 0.50 (t, J=7.4 Hz, 3H).

Workup

  1. additiondiluted in 1 mL of dry DMP at 0° C
  2. additionwas added dropwise
  3. stirringThe reddish solution was stirred to 0° C. until completion (TLC monitoring)
  4. temperatureAfter cooling
  5. extractionthe mixture as extracted with ethyl acetate
  6. washThe organic layer was washed with water and brine
  7. dry with materialdried over MgSO4
  8. customThe solvents were evaporated under reduced pressure
  9. customthe residual oil was purified over silica gel (eluent: ethyl acetate/hexane: 5/95)

Sources & evidence

ORD record
ord-5f5b26dd0bb04739994aa22b90804dd7
Source dataset
uspto-grants-2008_03
Patent number
US07348359B2

Reaction notes

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