Bromine → 4-(3-Bromo-4-methoxyphenyl)pyridine

HRID 1107287

Reaction equation

HRID 1107287 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:14]=[CH:13][N:12]=[CH:11][CH:10]=2)=[CH:5][CH:4]=1.[Br:15]Br>C(O)(=O)C.O.[Fe]>[Br:15][C:8]1[CH:7]=[C:6]([C:9]2[CH:10]=[CH:11][N:12]=[CH:13][CH:14]=2)[CH:5]=[CH:4][C:3]=1[O:2][CH3:1]

Participants

6

Reactant 2

HCID 24408Bromine2×HCID 6038134-(4-Methoxyphenyl)pyridine

Product 1

HCID 184760964-(3-Bromo-4-methoxyphenyl)pyridine

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolvent3×HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

4-(4-Methoxyphenyl)pyridine (1 g, 5.4 mmol) was dissolved in glacial acetic acid (6 ml). Iron powder (30 mg, 0.54 mmol) was added followed by a solution of bromine (0.36 ml) in glacial acetic acid (3 ml) slowly over 5 minutes. The resulting solution was stirred at 60° C. for 1 hour. A solution of bromine (0.13 ml) in glacial acetic acid (1 ml) was added and stirring was continued at 60° C. for 1.5 hours. The solution was allowed to cool to ambient temperature, diluted with water (20 ml). Excess bromine was destroyed by adding in sold sodium bisulphite until all the colour had disappeared. Solid sodium carbonate was added until the solution was basic and the resulting solution was then extracted with ethyl acetate (2×30 ml) and dried over sodium sulphate. Removal of the solvent gave an oil which was chromatographed on silica gel in diethyl ether giving the title compound as a clear oil (0.77 g, 54%). 1H NMR (250 MHz, CDCl3) δ 8.66-8.62 (2H, d, J=8.6 Hz), 7.87-7.86 (1H, d, J=2.2 Hz), 7.61-7.56 (1H, dd, J=8.5 Hz and 2.2 Hz), 7.48-7.46 (1H, d, J=8.5 Hz), 7.03-6.99 (2H, d, J=8.6 Hz), and 3.96 (3H, s). m/z (ES+) 264, 266 (M+1).

Workup

  1. stirringstirring
  2. waitwas continued at 60° C. for 1.5 hours
  3. temperatureto cool to ambient temperature
  4. customExcess bromine was destroyed
  5. additionby adding in sold sodium bisulphite until all the colour
  6. additionSolid sodium carbonate was added until the solution
  7. extractionthe resulting solution was then extracted with ethyl acetate (2×30 ml)
  8. dry with materialdried over sodium sulphate
  9. customRemoval of the solvent
  10. customgave an oil which
  11. customwas chromatographed on silica gel in diethyl ether giving the title compound as a clear oil (0.77 g, 54%)

Sources & evidence

ORD record
ord-c0291c66fe7945558e0d4f5c91b4d080
Source dataset
uspto-grants-2000_05
Patent number
US06060469

Linked notes

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