Nitrogen → 4-Bromo-2,5-dimethylaniline

HRID 988934Notes

Reaction equation

HRID 988934 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([N+:9]([O-])=O)=[CH:4][C:3]=1[CH3:12].N#N.O.NN>CO.[Ni]>[NH2:9][C:5]1[CH:4]=[C:3]([CH3:12])[C:2]([Br:1])=[CH:7][C:6]=1[CH3:8]

Participants

6

Reactant 3

HCID 947NitrogenHCID 24654Hydrazine hydrate (1:1)HCID 8258081-Bromo-2,5-dimethyl-4-nitrobenzene

Product 1

HCID 81671304-Bromo-2,5-dimethylanilineYield 87%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Procedure

316 g of 2-bromo-5-nitro-p-xylene were dissolved in 3000 ml of methanol, freshly produced Raney nickel (about 4 g) was added under a vigorous stream of N2, and the mixture was heated to reflux with vigorous stirring. 275 ml of hydrazine hydrate (80% in water) were then slowly added dropwise. When the dropwise addition was complete (duration about 5 hours), the mixture was refluxed for about a further 6 hours. The catalyst was filtered off, the methanol was removed in a rotary evaporator, the residue was taken up in ethyl acetate, and the solution was washed by shaking with water, dried and re-evaporated in a rotary evaporator. The resultant crude product was recrystallized from heptane, giving 238 g (87%) of pale-green crystals.

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux with vigorous stirring
  3. additionWhen the dropwise addition
  4. temperaturethe mixture was refluxed for about a further 6 hours
  5. filtrationThe catalyst was filtered off
  6. customthe methanol was removed in a rotary evaporator
  7. washthe solution was washed
  8. customdried
  9. customre-evaporated in a rotary evaporator
  10. customThe resultant crude product was recrystallized from heptane

Sources & evidence

ORD record
ord-3f8aed2e9e164f63ac282842a2eecc61
Source dataset
uspto-grants-2003_10
Patent number
US06638646B2

Reaction notes

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