Hydrogen Bromide → 2-Bromo-3-nitrotoluene

HRID 1995142Notes

Reaction equation

HRID 1995142 reaction equation
[CH3:1][C:2]1[CH:8]=[CH:7][CH:6]=[C:5]([N+:9]([O-:11])=[O:10])[C:3]=1N.N([O-])=O.[Na+].[BrH:16]>O>[Br:16][C:3]1[C:5]([N+:9]([O-:11])=[O:10])=[CH:6][CH:7]=[CH:8][C:2]=1[CH3:1]

Participants

5

Reactant 3

HCID 260Hydrogen Bromide2×HCID 112982-Methyl-6-nitroanilineHCID 23668193Sodium Nitrite

Product 1

HCID 2318282-Bromo-3-nitrotoluene

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A stirred solution of 2-methyl-6-nitroaniline (75.0 g, 0.493 mole) and 40 ml of hydrobromic acid (48% solution) in 135 ml of water was cooled to 0°. During a one hour period a solution of sodium nitrite (36.2 g, 0.51 mole) in 60 ml of water was added to the reaction mixture. The mixture was suction filtered through a sintered glass funnel, collecting the filtrate in a flask cooled by a dry ice-acetone bath. The filtrate was placed in a jacketed addition funnel cooled by a dry ice-acetone bath. During a five minute period this solution was added to a stirred mixture of cuprous bromide (77.8 g, 0.51 mole) in 165 ml of hydrobromic acid (48% solution). After complete addition, the mixture was stirred at room temperature for approximately 18 hours, heated at reflux for two hours, then steam distilled. The distillate was extracted with methylene chloride and the extract washed with 2 N aqueous sodium hydroxide, followed by several portions of saturated aqueous sodium chloride solution. The organic phase was passed through phase separation filter paper and evaporated under reduced pressure to give 1-bromo-2-methyl-6-nitrobenzene (17 g) as a solid.

Workup

  1. filtrationfiltered through a sintered glass funnel
  2. customcollecting the filtrate in a flask
  3. temperaturecooled by a dry ice-acetone bath
  4. customThe filtrate was placed in a jacketed addition funnel
  5. temperaturecooled by a dry ice-acetone bath
  6. additionAfter complete addition
  7. temperatureheated
  8. temperatureat reflux for two hours
  9. distillationsteam distilled
  10. extractionThe distillate was extracted with methylene chloride
  11. washthe extract washed with 2 N aqueous sodium hydroxide
  12. customThe organic phase was passed through phase separation
  13. filtrationfilter paper
  14. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-c95d3b4f1951420ca0765d0a1ae30963
Source dataset
uspto-grants-1983_09
Patent number
US04402973

Reaction notes

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