4-Hydroxybenzaldehyde → HCID 23288043, compound

HRID 367317Notes

Reaction equation

HRID 367317 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[H-].[Na+].[C:12]([O:15][C:16]1[C:17]([C:32]([CH3:35])([CH3:34])[CH3:33])=[CH:18][C:19]2[O:23][C:22]([CH2:25]I)([CH3:24])[CH2:21][C:20]=2[C:27]=1[C:28]([CH3:31])([CH3:30])[CH3:29])(=[O:14])[CH3:13].[Cl-].[NH4+]>CN(C)C=O>[C:12]([O:15][C:16]1[C:17]([C:32]([CH3:35])([CH3:34])[CH3:33])=[CH:18][C:19]2[O:23][C:22]([CH2:24][O:1][C:2]3[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=3)([CH3:25])[CH2:21][C:20]=2[C:27]=1[C:28]([CH3:31])([CH3:30])[CH3:29])(=[O:14])[CH3:13]

Participants

6

Reactant 4

HCID 1264-HydroxybenzaldehydeHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 154857225-Acetoxy-4,6-di-t-butyl-2-iodomethyl-2-methyl-2,3-dihydrobenzofuran

Product 1

HCID 23288043HCID 23288043, compoundYield 49.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Under a nitrogen atmosphere, a solution of 4.57 g of 4-hydroxybenzaldehyde in 70 ml of N,N-dimethylformamide was added dropwise to an ice-cooled suspension of 1.5 g of 60% oily sodium hydride in 50 ml of N,N-dimethylformamide and the mixture was stirred at room temperature for 30 minutes. Then, the reaction solution was cooled to 0° C. and a solution of 13.2 g of 5-acetoxy-4,6-di-t-butyl-2-iodomethyl-2-methyl-2,3-dihydrobenzofuran synthesized in Example 70-2) in 100 ml of N,N-dimethylformamide was added dropwise, and the mixture was heated under reflux for 6 hours. After cooling, the reaction solution was combined with a saturated aqueous ammonium chloride solution and extracted with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then concentrated. The concentrate was purified by silica gel column chromatography eluting with n-hexane containing 20% ethyl acetate to give 6.4 g of 5-acetoxy-4,6-di-t-butyl-2-(4-formylphenoxymethyl)-2-methyl-2,3-dihydrobenzofuran (rotamer mixture) as a colorless oil (yield 48%).

Workup

  1. temperaturecooled
  2. temperatureThen, the reaction solution was cooled to 0° C.
  3. temperaturethe mixture was heated
  4. temperatureunder reflux for 6 hours
  5. temperatureAfter cooling
  6. extractionextracted with ethyl acetate
  7. washthe organic layer was washed with saturated brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated
  10. customThe concentrate was purified by silica gel column chromatography
  11. washeluting with n-hexane containing 20% ethyl acetate

Sources & evidence

ORD record
ord-f5e72c8b446447ee9fad60031c6fee48
Source dataset
uspto-grants-2000_10
Patent number
US06133279

Reaction notes

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