Acetic Acid → 2-Bromo-4-methyl-5-nitroanisole

HRID 1283838Notes

Reaction equation

HRID 1283838 reaction equation
N[C:2]1[CH:3]=[C:4]([CH3:13])[C:5]([N+:10]([O-:12])=[O:11])=[CH:6][C:7]=1[O:8][CH3:9].C(O)(=O)C.[BrH:18].N([O-])=O.[Na+]>O>[Br:18][C:2]1[CH:3]=[C:4]([CH3:13])[C:5]([N+:10]([O-:12])=[O:11])=[CH:6][C:7]=1[O:8][CH3:9]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 260Hydrogen Bromide3×HCID 67253Benzenamine, 2-methoxy-5-methyl-4-nitro-HCID 23668193Sodium Nitrite

Product 1

HCID 2847442-Bromo-4-methyl-5-nitroanisoleYield 72%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent4×

Procedure

A slurry of 3-amino-4-methoxy-6-nitrotoluene (18 g) in water (20 ml) containing acetic acid (20 ml) and hydrobromic acid (47%, 35 ml) is stirred until a fine suspension of the hydrobromide is formed, cooled to 0°, and treated with a solution of sodium nitrite (7 g) in water (20 ml) added over 20 min. After a further 10 min., the yellow-brown solution is stirred into a mixture of cuprous bromide (30 g) and hydrobromic acid (47%, 30 ml) in water (50 ml), the mixture warmed on the steam bath until an effervescence commences and then at 70° for 1 hr. The mixture is cooled, diluted with water (500 ml), and the solid collected and recrystallized from aqueous ethanol to give a 3-bromo-4-methoxy-6-nitrotoluene (I) as pale yellow needles (18 g, 72%): mp 91-92°.

Workup

  1. customis formed
  2. temperaturecooled to 0°
  3. additionadded over 20 min
  4. temperaturethe mixture warmed on the steam bath until an effervescence commences
  5. waitat 70° for 1 hr
  6. temperatureThe mixture is cooled
  7. customthe solid collected
  8. customrecrystallized from aqueous ethanol

Sources & evidence

ORD record
ord-d23383b883dd4f1e8f6092283f31a15e
Source dataset
uspto-grants-1976_08
Patent number
US03976652

Reaction notes

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