1-Bromo-4-nitrobenzene → 1,1'-Biphenyl, 4-(1,1-dimethylethyl)-4'-nitro-

HRID 642800Notes

Reaction equation

HRID 642800 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[C:11]([C:15]1[CH:20]=[CH:19][C:18](B(O)O)=[CH:17][CH:16]=1)([CH3:14])([CH3:13])[CH3:12].[F-].[K+]>C1(C)C=CC=CC=1>[C:11]([C:15]1[CH:20]=[CH:19][C:18]([C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=2)=[CH:17][CH:16]=1)([CH3:14])([CH3:13])[CH3:12]

Participants

5

Reactant 3

HCID 114661-Bromo-4-nitrobenzeneHCID 522689Potassium FluorideHCID 27343204-tert-Butylphenylboronic acid

Product 1

HCID 30259791,1'-Biphenyl, 4-(1,1-dimethylethyl)-4'-nitro-Yield 70.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 1-bromo-4-nitro-benzene (2.02 g, 10 mmol) in toluene (20 mL) is added palladium tetrakis triphenylphosphine (1.156 g, 1 mmol), 4-t-butyl phenyl boronic acid (3.56 g, 20 mmol), and potassium fluoride (1.74 g, 30 mmol). The reaction is purged with nitrogen three times and heated to reflux under nitrogen. At the reflux temperature, water (5 mL) is added to the reaction and the reaction is allowed to reflux under nitrogen. The reaction is monitored by HPLC, and upon completion, allowed to cool to room temperature. The reaction is, diluted with ethyl acetate and Celite® is added, followed by water. This mixture is then filtered through a pad of Celite®. The solution is poured into a separatory funnel and the organic layer is washed with water and brine. The organic layer is dried over anhydrous sodium sulfate and concentrated. The resulting residue is purified by flash column chromatography, eluting with ethyl acetate/hexanes to afford 1.8 g of the product as a yellow solid. 1H-NMR.

Workup

  1. customThe reaction is purged with nitrogen three times
  2. temperatureheated
  3. temperatureto reflux under nitrogen
  4. additionAt the reflux temperature, water (5 mL) is added to the reaction
  5. temperatureto reflux under nitrogen
  6. additiondiluted with ethyl acetate and Celite®
  7. additionis added
  8. filtrationThis mixture is then filtered through a pad of Celite®
  9. additionThe solution is poured into a separatory funnel
  10. washthe organic layer is washed with water and brine
  11. dry with materialThe organic layer is dried over anhydrous sodium sulfate
  12. concentrationconcentrated
  13. customThe resulting residue is purified by flash column chromatography
  14. washeluting with ethyl acetate/hexanes

Sources & evidence

ORD record
ord-0fe43b63e9d44161923ef53735c914af
Source dataset
uspto-grants-2010_04
Patent number
US07696248B2

Reaction notes

Loading…