1-Bromo-4-nitrobenzene → 4-Nitro-1,1'-biphenyl

HRID 72092

Reaction equation

HRID 72092 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.C[Sn](C)(C)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C([O-])(=O)C.[NH4+]>COCCOC.CCOCC.CC([O-])=O.CC([O-])=O.[Pd+2]>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:3][CH:4]=1)([O-:10])=[O:9]

Participants

7

Reactant 3

HCID 114661-Bromo-4-nitrobenzeneHCID 123095Stannane, trimethylphenyl-HCID 517165Ammonium Acetate

Product 1

HCID 71144-Nitro-1,1'-biphenyl

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

Microencapsulated Pd(OAc)2 (prepared as described in Example 1, 0.25 g, 2 mol %, based on palladium content) was added to a solution of 4-bromo nitrobenzene (1 mmol), trimethylphenyltin (1.5 mmol) and ammonium acetate (3 mmol) in 1,2-dimethoxyethane (5 mL) and stirred at 90° C. for 6 h. The reaction mixture was cooled to room temperature, diluted with ether (50 mL) and filtered through a polyethylene frit (20-micron porosity). The filtrate was washed with water (2×20 mL), brine (20 mL) and dried (MgSO4). Evaporation under reduced pressure and purification by column chromatography gave 4-nitrobiphenyl, 90%: IR, 1H NMR and 13C NMR identical with sample obtained from the Suzuki reaction in Example 5.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered through a polyethylene frit (20-micron porosity)
  3. washThe filtrate was washed with water (2×20 mL), brine (20 mL)
  4. dry with materialdried (MgSO4)
  5. customEvaporation
  6. customunder reduced pressure and purification by column chromatography

Sources & evidence

ORD record
ord-bcc41ec5ffe04b37a6cbe788ee6e67b0
Source dataset
uspto-grants-2014_09
Patent number
US08828902B2

Linked notes

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