Dimethyl Sulfoxide → Methyl 5,5'-difluoro-2'-nitrobiphenyl-2-carboxylate

HRID 1966497Notes

Reaction equation

HRID 1966497 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].CS(C)=O.Br[C:17]1[CH:26]=[C:25]([F:27])[CH:24]=[CH:23][C:18]=1[C:19]([O:21][CH3:22])=[O:20]>C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[Cu]>[F:27][C:25]1[CH:24]=[C:23]([C:2]2[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=2[N+:9]([O-:11])=[O:10])[C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][CH:26]=1

Participants

7

Reactant 3

HCID 679Dimethyl SulfoxideHCID 27569932-Bromo-4-fluoro-1-nitrobenzeneHCID 7210837Methyl 2-bromo-4-fluorobenzoate

Product 1

HCID 67296874Methyl 5,5'-difluoro-2'-nitrobiphenyl-2-carboxylateYield 113.3%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To 2-bromo-4-fluoro-1-nitrobenzene (185.16 mg, 0.842 mmol) was added Pd2dba3 (23.12 mg, 0.025 mmol) and copper powder (271 mg, 4.26 mmol). Dimethylsulfoxide (2.3 ml) and methyl 2-bromo-4-fluorobenzoate (0.122 ml, 0.842 mmol) were added and the mixture was stirred vigorously at 100° C. for 2 h. The mixture was cooled to room temperature, diluted with ethyl acetate (20 ml), and filtered. The filtrate was washed with water and dried (anhydrous Na2SO4) and concentrated to give a yellow oil (279.8 mg). This oil was utilized without purification for the preparation of Example 38b.

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. filtrationfiltered
  3. washThe filtrate was washed with water
  4. dry with materialdried (anhydrous Na2SO4)
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-e260a73252e14908b3c8a6724e3c06a4
Source dataset
uspto-grants-2013_04
Patent number
US08420596B2

Reaction notes

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