Nitrogen → 1-(4-Chloro-3'-fluoro-5-methyl-6-nitrobiphenyl-2-yl)ethanone

HRID 1192705Notes

Reaction equation

HRID 1192705 reaction equation
FC(F)(F)S(O[C:7]1[C:12]([C:13](=[O:15])[CH3:14])=[CH:11][C:10]([Cl:16])=[C:9]([CH3:17])[C:8]=1[N+:18]([O-:20])=[O:19])(=O)=O.[F:23][C:24]1[CH:25]=[C:26](B(O)O)[CH:27]=[CH:28][CH:29]=1.N#N>C1(C)C=CC=CC=1.C([O-])(O)=O.[Na+].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:16][C:10]1[C:9]([CH3:17])=[C:8]([N+:18]([O-:20])=[O:19])[C:7]([C:28]2[CH:27]=[CH:26][CH:25]=[C:24]([F:23])[CH:29]=2)=[C:12]([C:13](=[O:15])[CH3:14])[CH:11]=1

Participants

7

Reactant 3

HCID 947NitrogenHCID 27339863-Fluorophenylboronic acidHCID 866561856-Acetyl-4-chloro-3-methyl-2-nitrophenyl trifluoromethanesulfonate

Product 1

HCID 866561861-(4-Chloro-3'-fluoro-5-methyl-6-nitrobiphenyl-2-yl)ethanoneYield 92.1%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
80 °C

Procedure

A biphasic solution of 6-acetyl-4-chloro-3-methyl-2-nitrophenyl trifluoromethanesulfonate (3.00 g, 8.29 mmol) and (3-fluorophenyl)boronic acid (1.74 g, 12.4 mmol) in toluene (80 mL) and saturated NaHCO3 (80 mL) was bubbled with N2 to degas. Tetrakis(triphenylphosphine)palladium(0) (0.479 g, 0.415 mmol) was added The reaction mixture was bubbled with N2 for 5 minutes more and heated at 80° C. for 2 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate. The layers were separated and the aq. layer was extracted with ethyl acetate. The combined extracts were washed with brine, dried over Na2SO4, filtered and concentrated. The resulting material was purified on silica gel column, eluting with ethyl acetate/hexane, 0-30%, to give the desired product (2.35 g, 92%). LCMS calculated for C15H12ClFNO3 (M+H)+: m/z=308.0; Found: 308.1.

Workup

  1. customto degas
  2. customwas bubbled with N2 for 5 minutes more
  3. temperatureAfter cooling to room temperature
  4. additionthe mixture was diluted with ethyl acetate
  5. customThe layers were separated
  6. extractionthe aq. layer was extracted with ethyl acetate
  7. washThe combined extracts were washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe resulting material was purified on silica gel column
  12. washeluting with ethyl acetate/hexane, 0-30%

Sources & evidence

ORD record
ord-4e7d489470184161905591129055cde9
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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