1,4-Dibromo-2-nitrobenzene → 4,4'-Dibromo-2,2'-dinitro-1,1'-biphenyl

HRID 1821060Notes

Reaction equation

HRID 1821060 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10]>CN(C=O)C.[Cu]>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([C:2]2[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][C:3]=2[N+:9]([O-:11])=[O:10])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

Participants

4

Reactant 1

HCID 770041,4-Dibromo-2-nitrobenzene

Product 1

HCID 100466484,4'-Dibromo-2,2'-dinitro-1,1'-biphenylYield 64.1%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
125 °C

Procedure

To a stirring solution of 2,5-dibromonitrobenzene (24.0 g, 85.4 mmol) in DMF (110 mL) was added copper powder (12.0 g, 188.9 mmol), and the reaction mixture was heated at 125° C. After 3 h, the mixture was allowed to cool to room temperature. After most of the DMF was evaporated under high vacuum at 60° C., the residue was dissolved in benzene (400 mL) and the insoluble inorganic salts and excess copper were removed by filtration through Celite®. The filtrate was washed with water and 10% NaHCO3 and evaporated to dryness to yield the crude product as yellow crystals (15.6 g, 91%). The crude product was next recrystallized from isopropanol to yield 11.0 g of pure product. The mother liquid was evaporated to one-fourth of its volume and an additional 3.9 g of pure product was recovered, giving a total yield of 14.9 g (87%). 1H NMR (CDCl3): δ 7.17 (2H, d, J=8.0), 7.84 (2H, dd, J=8.0, 2.0), 8.39 (2H, d, J=2.0) ppm; 13C NMR (CDCl3): δ 123.0, 128.2, 131.8, 132.0, 136.4, 147.5 ppm; m.p. 148° C.

Workup

  1. temperatureto cool to room temperature
  2. customAfter most of the DMF was evaporated under high vacuum at 60° C.
  3. dissolutionthe residue was dissolved in benzene (400 mL)
  4. customthe insoluble inorganic salts and excess copper were removed by filtration through Celite®
  5. washThe filtrate was washed with water and 10% NaHCO3
  6. customevaporated to dryness
  7. customto yield the crude product as yellow crystals (15.6 g, 91%)
  8. customThe crude product was next recrystallized from isopropanol

Sources & evidence

ORD record
ord-4c449f879d11410aac4442bc3857bd3e
Source dataset
uspto-grants-2009_10
Patent number
US07605225B2

Reaction notes

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