Potassium Carbonate → 4-Cyclopropyl-1-fluoro-2-nitrobenzene

HRID 1898322Notes

Reaction equation

HRID 1898322 reaction equation
[CH:1]1(B(O)O)[CH2:3][CH2:2]1.Br[C:8]1[CH:13]=[CH:12][C:11]([F:14])=[C:10]([N+:15]([O-:17])=[O:16])[CH:9]=1.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH:1]1([C:8]2[CH:13]=[CH:12][C:11]([F:14])=[C:10]([N+:15]([O-:17])=[O:16])[CH:9]=2)[CH2:3][CH2:2]1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 27363284-Bromo-1-fluoro-2-nitrobenzeneHCID 2760897Cyclopropylboronic acid

Product 1

HCID 569685734-Cyclopropyl-1-fluoro-2-nitrobenzeneYield 84.7%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolvent

Procedure

Degas the solution of cyclopropyl boronic acid (0.585 g, 6.80 mmol) in dry toluene (6 mL) for 30 minutes. Then added tetrakis(triphenylphosphine) Palladium (0.090 g, 0.089 mmol) and 4-bromo-1-fluoro-2-nitrobenzene (1.0 g, 4.56 mmol) to the solution. The reaction mass was again degassed for 30 minutes and then added potassium carbonate (0.0628 g, 4.55 mmol). The reaction mass was refluxed for 48 h. The excess of solvent was removed under vacuum and the reaction mass was quenched in water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulphate and concentrated. The obtained crude was purified by column chromatography to afford 0.700 g of the desired product. 1H NMR (300 MHz, DMSO d6): δ 0.74-0.76 (m, 2H), 1.00-1.02 (m, 2H), 2.08 (m, 1H), 7.45-7.48 (m, 2H), 7.83 (d, J=6.9 Hz, 1H); MS [M+H]+: 164.13.

Workup

  1. customThe reaction mass was again degassed for 30 minutes
  2. temperatureThe reaction mass was refluxed for 48 h
  3. customThe excess of solvent was removed under vacuum
  4. customthe reaction mass was quenched in water
  5. extractionextracted with ethyl acetate
  6. dry with materialThe organic layer was dried over anhydrous sodium sulphate
  7. concentrationconcentrated
  8. customThe obtained crude
  9. customwas purified by column chromatography

Sources & evidence

ORD record
ord-4bf23e584f434537bcc1dd9c7ccd295c
Source dataset
uspto-grants-2013_08
Patent number
US08519149B2

Reaction notes

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