1,3-Dibromobenzene → 3'-Bromo-2-methoxybiphenyl

HRID 45455

Reaction equation

HRID 45455 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1B(O)O.[Br:12][C:13]1[CH:14]=[CH:15][CH:16]=[C:17](Br)[CH:18]=1.C(=O)(O)[O-].[Na+]>COCCOC.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:12][C:13]1[CH:18]=[C:17]([C:4]2[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=2[O:2][CH3:1])[CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 3

HCID 79271,3-DibromobenzeneHCID 516892Sodium BicarbonateHCID 27339582-Methoxyphenylboronic acid

Product 1

HCID 186686213'-Bromo-2-methoxybiphenylYield 190.7%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A mixture of 2-methoxyphenylboronic acid (4.3 g, 28.3 mmol), 3,5-dibromobenzene (20 g, 85.5 mmol, 3 equiv.) and bis(triphenylphosphine)palladium(II) dichloride (100 mg) in ethyleneglycol dimethylether (25 mL) and a solution of sodium bicarbonate (8.2 g, 0.098 mol) in water (140 mL) were kept at reflux under nitrogen with good stirring overnight. After cooling, the reaction mixture was partitioned between ethyl acetate (600 mL) and water (300 mL). The organic phase was washed with water (2×300 mL), dried over sodium sulfate and filtered. The solvent was removed in vacuo and the crude product was purified by chromatography on silica (150 g) with heptane (6 L) to afford pure 21 (14.2 g, 58%).

Workup

  1. temperatureat reflux under nitrogen
  2. temperatureAfter cooling
  3. customthe reaction mixture was partitioned between ethyl acetate (600 mL) and water (300 mL)
  4. washThe organic phase was washed with water (2×300 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customThe solvent was removed in vacuo
  8. customthe crude product was purified by chromatography on silica (150 g) with heptane (6 L)

Sources & evidence

ORD record
ord-da2289bbb0d444e6a1e174ec6f92aef7
Source dataset
uspto-grants-2013_09
Patent number
US08541522B2

Linked notes

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