Ethanol → 4-Bromo-2-(3'-bromophenyl)-pyridine

HRID 43252Notes

Reaction equation

HRID 43252 reaction equation
Br[C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[CH:4][N:3]=1.[Br:9][C:10]1[CH:11]=[C:12](B(O)O)[CH:13]=[CH:14][CH:15]=1.C([O-])([O-])=O.[Na+].[Na+].CCO>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C)C=CC=CC=1>[Br:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([C:14]2[CH:13]=[CH:12][CH:11]=[C:10]([Br:9])[CH:15]=2)[CH:7]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 8171042,4-DibromopyridineHCID 2734318(3-Bromophenyl)boronic acid

Product 1

HCID 672133874-Bromo-2-(3'-bromophenyl)-pyridine

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 2,4-dibromopyridine (3.30 g, 13.9 mmol), 3-bromophenylboronic acid (3.69 g, 16.7 mmol), tetrakis(triphenylphosphine) palladium (0) (643 mg, 0.557 mmol), 2 M Na2CO3(aq) (12 cm3), EtOH (12 cm3) and toluene (40 cm3) was degassed and then heated at reflux with a bath temperature of 110° C. under argon for 3.5 days. The reaction was allowed to cool and the two phases were separated. The aqueous layer was extracted with ether (3×13 cm3). The organic layer and the ether extracts were combined, washed with brine (1×30 cm3) and dried over anhydrous sodium sulfate. The solvents were completely removed to leave a black brown oil. The oil was purified by column chromatography over silica gel using DCM-light petroleum (0:1 to 1:10) as eluent to give 1.03 g (24%) of A-6 as a white solid; δH(200 MHz; CDCl3) 7.36 (1 H, m, ArH), 7.45 (1 H, m, PyH), 7.58 (1 H, m, ArH), 7.89 (2 H, m, PyH & ArH), 8.16 (1 H, m, ArH), and 8.52 (1 H, m, PyH); m/z [APCI+]311, 314, 316 (MH+).

Workup

  1. customwas degassed
  2. temperatureheated
  3. temperatureto cool
  4. customthe two phases were separated
  5. extractionThe aqueous layer was extracted with ether (3×13 cm3)
  6. washwashed with brine (1×30 cm3)
  7. dry with materialdried over anhydrous sodium sulfate
  8. customThe solvents were completely removed
  9. customto leave a black brown oil
  10. customThe oil was purified by column chromatography over silica gel
  11. customto give 1.03 g (24%) of A-6 as a white solid

Sources & evidence

ORD record
ord-62354dc1a19b439eac79130b0cc6ac92
Source dataset
uspto-grants-2013_09
Patent number
US08536333B2

Reaction notes

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