Sulfuric Acid → 5-Bromo-2-tert-butylphenol

HRID 635560Notes

Reaction equation

HRID 635560 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([OH:8])[CH:5]=[CH:6][CH:7]=1.[CH3:9][C:10](O)([CH3:12])[CH3:11].S(=O)(=O)(O)O.C([O-])(O)=O.[Na+]>C(Cl)(Cl)(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:10]([CH3:12])([CH3:11])[CH3:9])=[C:4]([OH:8])[CH:3]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 6386tert-ButanolHCID 115633-BromophenolHCID 516892Sodium Bicarbonate

Product 1

HCID 103313825-Bromo-2-tert-butylphenol

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 29.5 g (170.3 mmol) of 3-bromophenol in 100 mL of carbon tetrachloride (under a blanket of argon) was added 16.4 g (221.3 mmol) of 2-methyl-2-propanol followed by 20 mL of conc. sulfuric acid. The reaction mixture was allowed to stir at ambient temperature for 3.5 days. The clear, colorless solution turned pink and eventually turned purple in color. The reaction mixture was neutralized with sat. NaHCO3 (aq.) solution and then extracted between water and dichloromethane. The layers were separated and the aqueous phase was washed with dichloromethane. The organic phases were combined and washed with brine, dried over MgSO4, filtered and concentrated in vacuo to a purple oil. Purification by flash chromatography (silica, 5% ethyl acetate in hexane) followed by kugelrohr distillation (85-95° C., 2 mm Hg) gave the title compound as a clear, slightly yellow oil. PMR (CDCl3): δ 1.38 (9 H, s), 4.93 (1 H, s), 6.84 (1 H, d, J=2.1 Hz), 6.99 (1 H, dd, J=2.1, 8.2 Hz), 7.12 (1 H, d, J=8.2 Hz).

Workup

  1. extractionextracted between water and dichloromethane
  2. customThe layers were separated
  3. washthe aqueous phase was washed with dichloromethane
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo to a purple oil
  8. customPurification by flash chromatography (silica, 5% ethyl acetate in hexane)
  9. distillationfollowed by kugelrohr distillation (85-95° C., 2 mm Hg)

Sources & evidence

ORD record
ord-367702a02d4c4ba7ac08eeeaedebc3e6
Source dataset
uspto-grants-2001_02
Patent number
US06187950B1

Reaction notes

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