Nitrogen → 1-(2-Bromophenyl)naphthalene

HRID 1049636Notes

Reaction equation

HRID 1049636 reaction equation
C(=O)([O-])[O-].[K+].[K+].[Br:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1B(O)O.Br[C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20][CH:19]=1.N#N.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)C.COCCOC.O>[Br:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[C:26]1[C:27]2[C:22](=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:23]=[CH:24][CH:25]=1

Participants

10

Reactant 5

HCID 947NitrogenHCID 70011-BromonaphthaleneHCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 2773294(2-Bromophenyl)boronic acid

Product 1

HCID 118329071-(2-Bromophenyl)naphthaleneYield 52.5%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
85 °C

Procedure

To a 250-mL round bottom flask equipped with a magnetic stir bar was added water (25 mL) and 1,2-dimethoxyethane (25 mL). The solution was sparged with nitrogen for 20 minutes, then potassium carbonate (6.67 g, 48.3 mmol, 3 equiv), 2-bromophenylboronic acid (3.80 g, 18.9 mmol, 0.98 equiv) and 1-bromonaphthalene (2.70 mL, 19.3 mmol, 1 equiv) were added. The flask was then purged with N2 for 10 minutes before finally adding palladium(II)acetate (87 mg, 0.39 mmol, 0.02 equiv) and triphenylphosphine (405 mg, 1.55 mmol, 0.08 equiv). The reaction mixture was heated to 85° C. under a positive pressure of nitrogen for 16 hours. After cooling to room temperature, the phases were partitioned and the organic layer was collected, and the aqueous layer was washed with ethyl acetate (3×20 mL). The combined organic fractions were washed with brine (50 mL), dried over sodium sulfate, filtered, and concentrated on a rotary evaporator. The crude material was purified by column chromatography on an Isco CombiFlash system (120-g column; gradient: ramp up from heptane to 99:1 heptane:ethyl acetate over 1.5 column volumes, hold at 99:1 for 1.5 column volumes, ramp up to 92:8 heptane:ethyl acetate over 6 column volumes, hold at 92:8 for 6 column volumes) and then recrystallization from 99:1 heptane:ethanol to afford the title compound as a white solid (2.81 g, 93 area % by HPLC, 51% yield). 1H NMR (400 MHz, CDCl3) δ ppm 7.91 (dd, J=8.3, 0.8 Hz, 2H), 7.74 (dd, J=8.0, 1.2 Hz, 1H), 7.57-7.29 (m, 8H)

Workup

  1. customTo a 250-mL round bottom flask equipped with a magnetic stir bar
  2. customThe solution was sparged with nitrogen for 20 minutes
  3. temperatureAfter cooling to room temperature
  4. customthe phases were partitioned
  5. customthe organic layer was collected
  6. washthe aqueous layer was washed with ethyl acetate (3×20 mL)
  7. washThe combined organic fractions were washed with brine (50 mL)
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated on a rotary evaporator
  11. customThe crude material was purified by column chromatography on an Isco CombiFlash system (120-g column
  12. customrecrystallization from 99:1 heptane

Sources & evidence

ORD record
ord-a87d098ffdc14a208d4e0c8d37a10662
Source dataset
uspto-grants-2016_07
Patent number
US09381508B2

Reaction notes

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