4-Bromoaniline → Benzenamine, 4-(1-naphthalenyl)-

HRID 2191072Notes

Reaction equation

HRID 2191072 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[C:9]1(B(O)O)[C:18]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:12]=[CH:11][CH:10]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)([O-])[O-].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C1(C)C=CC=CC=1.C(O)C>[C:17]1([C:2]2[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=2)[C:18]2[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:14]=[CH:15][CH:16]=1

Participants

9

Reactant 4

HCID 78074-BromoanilineHCID 11430Potassium CarbonateHCID 80271Tri-o-tolylphosphineHCID 2545321-Naphthaleneboronic acid

Product 1

HCID 2760169Benzenamine, 4-(1-naphthalenyl)-

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
60 °C

Procedure

First, 5.0 g (29 mmol) of 4-bromoaniline, 5.0 g (29 mmol) of 1-naphthylboronic acid, and 0.45 g (1.5 mmol) of tri(ortho-tolyl)phosphine were put into a 500-mL three-neck flask, and the air in the flask was replaced with nitrogen. Then, 100 mL of toluene, 50 mL of ethanol, and 31 mL of a potassium carbonate aqueous solution (2 mol/L) were added to this mixture. The mixture in the flask was stirred and degassed while reducing pressure in the flask. Then, after the mixture was heated at 60° C., 66.2 mg (0.29 mmol) of palladium(II) acetate was added to the mixture. The mixture was refluxed at 80° C. for 2.3 hours. After the reflux, toluene and water were added to the mixture, an organic layer and an aqueous layer were separated, and the aqueous layer was extracted twice with toluene. The extract and the organic layer were combined, washed with a saturated saline solution, and dried with magnesium sulfate. The mixture was subjected to gravity filtration to remove magnesium sulfate. Then, the filtrate was concentrated to give an oily substance, which was subjected to suction filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina to obtain a filtrate. The resulting filtrate was concentrated to give 2.5 g of an oily substance, which was an object, in a yield of 40%.

Workup

  1. customdegassed
  2. temperatureThe mixture was refluxed at 80° C. for 2.3 hours
  3. customan organic layer and an aqueous layer were separated
  4. extractionthe aqueous layer was extracted twice with toluene
  5. extractionThe extract
  6. washwashed with a saturated saline solution
  7. dry with materialdried with magnesium sulfate
  8. filtrationThe mixture was subjected to gravity filtration
  9. customto remove magnesium sulfate
  10. concentrationThen, the filtrate was concentrated
  11. customto give an oily substance, which
  12. filtrationwas subjected to suction filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina
  13. customto obtain a filtrate
  14. concentrationThe resulting filtrate was concentrated
  15. customto give 2.5 g of an oily substance, which

Sources & evidence

ORD record
ord-763a9c53a69e4b38af4adac7392b0f60
Source dataset
uspto-grants-2012_12
Patent number
US08324615B2

Reaction notes

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