Cyclohexylphosphine → 4-Cyclopropyl-2-nitroaniline

HRID 227160Notes

Reaction equation

HRID 227160 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[CH:12]1(B(O)O)[CH2:14][CH2:13]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(P)CCCCC1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH:12]1([C:2]2[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=2)[CH2:14][CH2:13]1

Participants

8

Reactant 4

HCID 13199CyclohexylphosphineHCID 62657Potassium Phosphate, TribasicHCID 701324-Bromo-2-nitroanilineHCID 2760897Cyclopropylboronic acid

Product 1

HCID 222249274-Cyclopropyl-2-nitroanilineYield 143.8%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

4-Bromo-2-nitroaniline (2.17 g, 10 mmol), cyclopropylboronic acid (1.12 g, 1.30 mmol), potassium phosphate (7.42 g, 35 mmol), palladium (II) acetate (120 mg, 0.5 mmol), and cyclohexylphosphine (280 mg, 1 mmol) were combined in toluene (40 mL) and water (2 mL) and heated on an oil bath at 100° C. for 16 hours. The mixture was cooled, and the mixture was triturated with dichloromethane and water. The resulting mixture was filtered through a pad of celite. The organic layer of the filtrate was separated and dried over anhydrous sodium sulfate. Concentration gave an oil that was chromatographed over silica gel (30% v/v diethyl ether in hexanes). The faster moving compound was collected and the solvent was concentrated to give an orange oil. The oil was dissolved in hot hexanes/ethyl acetate and cooling gave 4-cyclopropyl-2-nitroaniline as orange needles (333 mg, 1.87 mmol, 19% ).

Workup

  1. temperatureThe mixture was cooled
  2. customthe mixture was triturated with dichloromethane and water
  3. filtrationThe resulting mixture was filtered through a pad of celite
  4. customThe organic layer of the filtrate was separated
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationConcentration
  7. customgave an oil that
  8. customwas chromatographed over silica gel (30% v/v diethyl ether in hexanes)
  9. customwas collected
  10. concentrationthe solvent was concentrated
  11. customto give an orange oil
  12. temperaturecooling

Sources & evidence

ORD record
ord-ca64e5dc8b5e48688f4342d841cf1ff1
Source dataset
uspto-grants-2009_07
Patent number
US07557221B2

Reaction notes

Loading…