Sodium Carbonate → 2,4'-Difluoro-6-nitro-1,1'-biphenyl

HRID 1776198Notes

Reaction equation

HRID 1776198 reaction equation
Cl[C:2]1[C:7]([F:8])=[CH:6][CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].[F:12][C:13]1[CH:18]=[CH:17][C:16](B(O)O)=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Na+].[Na+].[OH-].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.O1CCOCC1.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C(OCC)C>[F:8][C:7]1[CH:6]=[CH:5][CH:4]=[C:3]([N+:9]([O-:11])=[O:10])[C:2]=1[C:16]1[CH:17]=[CH:18][C:13]([F:12])=[CH:14][CH:15]=1

Participants

10

Reactant 4

HCID 10340Sodium CarbonateHCID 14798Sodium HydroxideHCID 888832-Chloro-1-fluoro-3-nitrobenzeneHCID 2856454-Fluorophenylboronic acid

Product 1

HCID 463126122,4'-Difluoro-6-nitro-1,1'-biphenylYield 57.5%

Reagents, catalysts & solvents 5

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A microwave reaction vessel was charged with 2-chloro-3-fluoronitrobenzene (1.500 g, 8.5 mmol), 4-fluorophenylboronic acid (1.315 g, 9.4 mmol), sodium carbonate (2.717 g, 25.6 mmol), palladium diacetate (0.077 g, 0.3 mmol), tetrabutylammonium bromide (2.755 g, 8.5 mmol) in water (10 mL) and 1,4-dioxane (1 mL). The mixture was heated to 100° C. in a microwave reactor for 1 hr. The reaction was cooled to room temperature and poured into diethyl ether and 0.1N aqueous sodium hydroxide. The organic layer was washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (10-30% methylene chloride/hexanes) to give the desired product as a yellow solid (1.15 g, 57%). 1H NMR (CDCl3, 300 MHz) δ 7.70 (dt, 1H, J=8.4, 1.5 Hz), 7.51 (td, 1H, J=8.4, 5.4 Hz), 7.41 (td, 1H, J=8.4, 1.2 Hz), 7.35-7.26 (m, 2H), 7.22-7.11 (m, 2H).

Workup

  1. customA microwave reaction vessel
  2. temperatureThe reaction was cooled to room temperature
  3. washThe organic layer was washed with saturated aqueous sodium chloride
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel chromatography (10-30% methylene chloride/hexanes)

Sources & evidence

ORD record
ord-268505bdae854de2b3dbc106dcb9d4d4
Source dataset
uspto-grants-2016_02
Patent number
US09265772B2

Reaction notes

Loading…