Benzene, 1-bromo-3-nitro- → 2-Chloro-6-fluoro-3'-nitro-1,1'-biphenyl

HRID 1527530Notes

Reaction equation

HRID 1527530 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[C:13]=1B(O)O.[F-].[K+]>O1CCOCC1.O.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[C:13]=1[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1

Participants

8

Reactant 3

HCID 11457Benzene, 1-bromo-3-nitro-HCID 522689Potassium FluorideHCID 35493952-Chloro-6-fluorophenylboronic acid2×

Product 1

HCID 682843732-Chloro-6-fluoro-3'-nitro-1,1'-biphenyl

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 1-bromo-3-nitrobenzene [585-79-5] (400 mg, 1.98 mmol) and 2-chloro-6-fluorophenylboronic acid [313545-32-3] (414 mg, 2.37 mmol) in dioxane (12 mL) and water (3 mL) was added potassium fluoride (460 mg, 7.92 mmol) and Pd(PPh3)4 (229 mg, 0.20 mmol). The solution was heated for 60 min at 120° C. under microwave irradiation. More 2-chloro-6-fluorophenylboronic acid (414 mg, 2.37 mmol) was added to the mixture followed by heating at 120° C. for 45 min under microwave irradiation. The reaction mixture was then diluted with EtOAc and the resulting solution was washed successively with saturated aqueous NaHCO3 solution and brine, the organics were then dried (Phase separator) and concentrated under reduced pressure. The residue was purified by preparative HPLC (Waters Sunfire, C18-ODB, 5 μm, 30×100 mm, flow: 50 mL/min, eluent: 20-100% CH3CN/H2O/20 min, 100% CH3CN/2 min, CH3CN and H2O containing 0.1% TFA) to give the title compound. tR (HPLC conditions c): 5.42 min.

Workup

  1. temperatureby heating at 120° C. for 45 min under microwave irradiation
  2. washthe resulting solution was washed successively with saturated aqueous NaHCO3 solution and brine
  3. customthe organics were then dried (Phase separator)
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by preparative HPLC (Waters Sunfire, C18-ODB, 5 μm, 30×100 mm, flow: 50 mL/min, eluent: 20-100% CH3CN/H2O/20 min, 100% CH3CN/2 min, CH3CN and H2O containing 0.1% TFA)

Sources & evidence

ORD record
ord-94ac9597a760400088e06c3a9a423f4d
Source dataset
uspto-grants-2015_07
Patent number
US09085555B2

Reaction notes

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