Phenol → 4-Bromo-2-methylphenol

HRID 1936331Notes

Reaction equation

HRID 1936331 reaction equation
S(=O)(=O)(O)O.[Br:6][C:7]1[CH:13]=[CH:12][C:10](N)=[C:9]([CH3:14])[CH:8]=1.N([O-])=[O:16].[Na+].NC(N)=O.S([O-])([O-])(=O)=O.[Na+].[Na+].C1(O)C=CC=CC=1>O>[Br:6][C:7]1[CH:13]=[CH:12][C:10]([OH:16])=[C:9]([CH3:14])[CH:8]=1

Participants

8

Reactant 6

HCID 996PhenolHCID 1118Sulfuric Acid2×HCID 1176UreaHCID 114234-Bromo-2-methylanilineHCID 24436Sodium SulfateHCID 23668193Sodium Nitrite

Product 1

HCID 168964-Bromo-2-methylphenolYield 69.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent4×

Procedure

First, 70 ml of water, 25 ml of concentrated sulfuric acid, and 25.0 g of 4-bromo-2-methylaniline were put in a 500 ml flask. After 60 g of ice was added, 30 ml of water containing 10.9 g of sodium nitrite dissolved therein was dropped in 25 minutes keeping the temperature at 5° C. or less. Another 100 ml of water, 100 g of ice, and 1 g of urea were added and the resultant mixture was left for 30 minutes. Then, 50 g of anhydrous sodium sulfate, 70 ml of concentrated sulfuric acid, and 33 ml of water were put in a 500 ml flask provided with a distiller, and heated to a temperature of 130° C. to 135° C. The former reaction solution was dropped into the resultant mixture, and phenol generating was distilled together with steam. Ether was added to the distilled solution for extraction. The resultant ether layer was washed with water and a sodium hydrogencarbonate aqueous solution. A 10% sodium hydroxide aqueous solution was further added for extraction. Then, 35 ml of concentrated hydrochloric acid was added to the resultant sodium hydroxide aqueous solution to acidify the solution, and ether was added for extraction. The resultant ether layer was washed with water and dried with anhydrous sodium sulfate. The solvent was then distilled off under decompression. The residue was distilled (b.p.: 135° C. to 139° C./8 mmHg) to obtain 17.48 g (Y: 69.7%) of 4-bromo-2-methylphenol. The purity of the resultant compound was 98.8% as measured by GC.

Workup

  1. additiontherein was dropped in 25 minutes
  2. customat 5° C. or less
  3. customprovided with a distiller
  4. temperatureheated to a temperature of 130° C. to 135° C
  5. distillationwas distilled together with steam
  6. additionEther was added to the distilled solution for extraction
  7. washThe resultant ether layer was washed with water
  8. additionA 10% sodium hydroxide aqueous solution was further added for extraction
  9. additionThen, 35 ml of concentrated hydrochloric acid was added to the resultant sodium hydroxide aqueous solution
  10. additionwas added for extraction
  11. washThe resultant ether layer was washed with water
  12. dry with materialdried with anhydrous sodium sulfate
  13. distillationThe solvent was then distilled off under decompression
  14. distillationThe residue was distilled (b.p.: 135° C. to 139° C./8 mmHg)

Sources & evidence

ORD record
ord-f2cc48a0d14f43dba958162ef540af64
Source dataset
uspto-grants-2002_05
Patent number
US06388146B1

Reaction notes

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