Ethanol → Ethyl 4-(2,5-dibromo-4-hydroxy-3-methoxyphenyl)-3,3-dimethylbutanoate

HRID 1860675Notes

Reaction equation

HRID 1860675 reaction equation
[Br:1][C:2]1[C:7]([O:8][CH3:9])=[C:6]([OH:10])[C:5]([Br:11])=[CH:4][C:3]=1[CH2:12][C:13]([CH3:18])([CH3:17])[CH2:14][CH:15]=[O:16].[OH-].[Na+].[CH2:21]([OH:23])[CH3:22]>O.[N+]([O-])([O-])=O.[Ag+]>[Br:1][C:2]1[C:7]([O:8][CH3:9])=[C:6]([OH:10])[C:5]([Br:11])=[CH:4][C:3]=1[CH2:12][C:13]([CH3:18])([CH3:17])[CH2:14][C:15]([O:23][CH2:21][CH3:22])=[O:16]

Participants

6

Reactant 3

HCID 702EthanolHCID 14798Sodium HydroxideHCID 186241724-(2,5-Dibromo-4-hydroxy-3-methoxyphenyl)-3,3-dimethylbutanal

Product 1

HCID 18624190Ethyl 4-(2,5-dibromo-4-hydroxy-3-methoxyphenyl)-3,3-dimethylbutanoate

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 962WaterSolvent2×

Procedure

A solution of Silver Nitrate (0.722 g, 4.25 mmol) in 2.0 ml H2O was added to a solution of the product of STEP 4 (0.775 g, 2.04 mmol) in 20 ml ethanol. A solution of sodium hydroxide (2.71 g, 67.7 mmol) in 3.0 ml H2O was added dropwise at room temperature. After 6 h, the reaction was filtered through a short column of Celite® and washed with H2O. The filtrate was extracted with ether (3×30 ml). The aqueous layer was acidified with concentrated HCl and extracted with chloroform. The organic layer was dried with MgSO4, concentrated and dried in vacuo. The residue (0.75 g) was dissolved in 15 ml ethanol and 15 ml 4N HCl in dioxane. The reaction was stirred at room temperature for 18 h and concentrated. The residue was purified by chromatography (on silica gel, ethyl acetate/hexane=3/7) to afford a pale brown oil in 0.536 g. NMR spectra of the product were consistent for the proposed structure.

Workup

  1. filtrationthe reaction was filtered through a short column of Celite®
  2. washwashed with H2O
  3. extractionThe filtrate was extracted with ether (3×30 ml)
  4. extractionextracted with chloroform
  5. dry with materialThe organic layer was dried with MgSO4
  6. concentrationconcentrated
  7. customdried in vacuo
  8. dissolutionThe residue (0.75 g) was dissolved in 15 ml ethanol
  9. concentrationconcentrated
  10. customThe residue was purified by chromatography (on silica gel, ethyl acetate/hexane=3/7)
  11. customto afford a pale brown oil in 0.536 g

Sources & evidence

ORD record
ord-0eefaaec7d044c0d8e0fa4e85c8069fa
Source dataset
uspto-grants-2003_03
Patent number
US06531494B1

Reaction notes

Loading…