Potassium Phosphate, Tribasic → 4-Cyclopropyl-2-fluoro-1-nitrobenzene

HRID 1411414Notes

Reaction equation

HRID 1411414 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([F:11])[CH:3]=1.[CH:12]1(B(O)O)[CH2:14][CH2:13]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=CC=1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.F[B-](F)(F)F.C1([PH+](C2CCCCC2)C2CCCCC2)CCCCC1>[CH:12]1([C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([F:11])[CH:3]=2)[CH2:14][CH2:13]1

Participants

7

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 2760897Cyclopropylboronic acidHCID 27833624-Bromo-2-fluoro-1-nitrobenzene

Product 1

HCID 574239144-Cyclopropyl-2-fluoro-1-nitrobenzeneYield 92.9%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 11710396Tricyclohexylphosphonium TetrafluoroborateCatalystHCID 22272177Toluene waterSolvent

Conditions

Temperature
85 °C

Procedure

A solution of 4-bromo-2-fluoronitrobenzene (0.5 g, 2.27 mmol), cyclopropylboronic acid (0.293 g, 3.41 mmol), tribasic potassium phosphate (0.965 g, 4.55 mmol), tricyclohexylphosphonium tetrafluoroborate (0.021 g, 0.057 mmol) and palladium (II) acetate (6.12 mg 0.027 mmol) in 11 mL of a toluene-water mixture 10:1 (v/v) was nitrogen purged-vacuum degassed three times. The reaction mixture was then heated in an oil bath at 85° C. for four hours. The reaction mixture was partitioned with ethyl acetate and the organic phase water washed then dried (Na2SO4) and concentrated. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was washed with water, dried (Na2SO4) and concentrated. The crude product was purified by chromatography on silica gel (ethyl acetate-hexane) to provide the title compound (0.382 g, 88%) as a yellow oil.

Workup

  1. customdegassed three times
  2. customThe reaction mixture was partitioned with ethyl acetate
  3. washthe organic phase water washed
  4. dry with materialthen dried (Na2SO4)
  5. concentrationconcentrated
  6. customThe reaction mixture was partitioned between ethyl acetate and water
  7. washThe organic phase was washed with water
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated
  10. customThe crude product was purified by chromatography on silica gel (ethyl acetate-hexane)

Sources & evidence

ORD record
ord-c8c0e1f8c5a144559a81a7b9780cabcb
Source dataset
uspto-grants-2014_12
Patent number
US08921514B2

Reaction notes

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