4-Methyl-2-nitroaniline → 4-Bromo-5-methylbenzene-1,2-diamine

HRID 2239256Notes

Reaction equation

HRID 2239256 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([N+:9]([O-])=O)[CH:3]=1.C1C(=O)N([Br:19])C(=O)C1>C(O)(=O)C.O.[Zn]>[Br:19][C:7]1[CH:6]=[C:5]([NH2:8])[C:4]([NH2:9])=[CH:3][C:2]=1[CH3:1]

Participants

6

Reactant 2

HCID 69784-Methyl-2-nitroanilineHCID 67184N-bromobutanimide

Product 1

HCID 224781204-Bromo-5-methylbenzene-1,2-diamineYield 83.2%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

To the solution of 4-methyl-2-nitro-phenylamine (1 g, 1 eq.) in 15 mL of acetic acid was added NBS (1.4 g, 1.2 eq.). The reaction was allowed to stir for 2.5 hours. Reaction was then diluted with 15 mL of water and Zn dust (1.29 g, 3 eq.) was added. Reaction was stirred for 1 hour, filtered and then pH was adjusted to ˜7 with ammonia. The aqueous layer was extracted with CH2Cl2 twice, dried over Na2SO4, concentrated and adsorbed on silica. Purification by flash column chromatography (60:40 hexanes/EtOAc) afforded 1.1 g (83 %) of product as off-white solid. MS (electrospray): mass calculated for C7H9BrN2, 201.06; m/z found 202.2, [M+H]+.

Workup

  1. customReaction
  2. additionwas added
  3. customReaction
  4. stirringwas stirred for 1 hour
  5. filtrationfiltered
  6. extractionThe aqueous layer was extracted with CH2Cl2 twice
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customPurification by flash column chromatography (60:40 hexanes/EtOAc)

Sources & evidence

ORD record
ord-d477910368594a9b96b4966c37cd8f96
Source dataset
uspto-grants-2010_05
Patent number
US07723326B2

Reaction notes

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