Sulfuric Acid → 3-Bromo-4-methylphenol

HRID 6907

Reaction equation

HRID 6907 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[CH3:9])N.[OH:10]S(O)(=O)=O.N([O-])=O.[Na+]>O>[Br:1][C:2]1[CH:3]=[C:4]([OH:10])[CH:6]=[CH:7][C:8]=1[CH3:9]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 82187Benzenamine, 3-bromo-4-methyl-HCID 23668193Sodium Nitrite

Product 1

HCID 103079133-Bromo-4-methylphenolYield 34%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a 0° C. mixture of 3-bromo-4-methyl aniline (5 g; 27 mmol) and H2SO4 (5.5 mL of a 16 M solution) in H2O (7.5 mL) was added dropwise a solution of aqueous NaNO2 (1.93 g; 28 mmol in 7.5 mL H2O). The reaction was stirred at 0° C. for 30 min, then was heated at 50° C. for 2 h, then was cooled to RT and extracted with EtOAc (2×). The combined organic extracts were washed with H2O, dried (Na2SO4) and concentrated in vacuo to give 3-bromo-4-methyl phenol (1.72 g; 34%) as an oil. This phenol was converted to 3-bromo-4-methyl phenyl chloroformate (1.9 g; 82%) using the same procedure (phosgene/dimethylaniline/heat) as for 3-fluoro-4-methyl phenyl chloroformate above.

Workup

  1. temperaturewas heated at 50° C. for 2 h
  2. temperaturewas cooled to RT
  3. extractionextracted with EtOAc (2×)
  4. washThe combined organic extracts were washed with H2O
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-03e350e0a3fc454085162cb70907dbec
Source dataset
uspto-grants-2006_08
Patent number
US07084162B2

Linked notes

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