Acetic Acid → 2-Bromo-4-chloro-6-methylbenzenamine

HRID 913826

Reaction equation

HRID 913826 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([CH3:9])[CH:3]=1.[Br-:10].[K+].C(O)(=O)C.B1([O-])OO1.O.O.O.O.[Na+].C(=O)(O)[O-].[Na+]>N.N.N.N.N.N.O.O.O.O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O>[Br:10][C:7]1[CH:8]=[C:2]([Cl:1])[CH:3]=[C:4]([CH3:9])[C:5]=1[NH2:6]

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 72514-Chloro-2-toluidineHCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrate

Product 1

HCID 205437542-Bromo-4-chloro-6-methylbenzenamine

Reagents, catalysts & solvents 2

HCID 16211167Ammonium paramolybdate tetrahydrateCatalystHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

4-Chloro-2-methylaniline (1.0 g, 7.06 mmol), potassium bromide (1.01 g, 8.47 mmol), and ammonium heptamolybdate tetrahydrate (87 mg, 0.07 mmol) were suspended in acetic acid (7 mL, 122 mmol) and cooled to 0° C. The reaction was treated with sodium perborate tetrahydrate (1.2 g, 7.77 mmol), stirred at 0° C. for 30 min, and at room temperature for 2 h. The mixture was poured into water, neutralized with saturated sodium bicarbonate and extracted with ethyl acetate (2×). The organic layers were pooled together, washed with brine (2×), dried over sodium sulfate, and concentrated to afford 1.2 g (78%). 1H-NMR (CDCl3, 500 MHz) δ 7.28 (s, 1H), 6.97 (s, 1H), 4.03 (bs, 2H), 2.17 (s, 3) Mass spec.: 221.90 (MH)+.

Workup

  1. waitat room temperature for 2 h
  2. extractionextracted with ethyl acetate (2×)
  3. washwashed with brine (2×)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customto afford 1.2 g (78%)

Sources & evidence

ORD record
ord-b3bb722067144d10a04789b67aeacb86
Source dataset
uspto-grants-2011_09
Patent number
US08026257B2

Linked notes

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