2-Bromonaphthalene → 2-(4-Bromophenyl)naphthalene

HRID 129790Notes

Reaction equation

HRID 129790 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH:3]=1.C([Li])(C)(C)C.[Br:17][C:18]1[CH:23]=[CH:22][C:21](I)=[CH:20][CH:19]=1>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:17][C:18]1[CH:23]=[CH:22][C:21]([C:2]2[CH:11]=[CH:10][C:9]3[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=3)[CH:3]=2)=[CH:20][CH:19]=1

Participants

6

Reactant 3

HCID 113722-BromonaphthaleneHCID 115221-Bromo-4-iodobenzeneHCID 178418306HCID 178418306, compound

Product 1

HCID 54617522-(4-Bromophenyl)naphthaleneYield 72%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 4.14 g (20.0 mmol) of 2-bromonaphthalene in 50 mL of THF at -78° C. under nitrogen was added a solution of 23.5 mL (40.0 mmol, 1.7M in pentane) of t-butyllithium over 10 minutes. The resulting slurry was stirred for 30 minutes and then warmed to 0° C. for 15 minutes. To this deep indigo solution was added a solution of 3.50 g (25.6 mmol) of thrice-fused zinc chloride in 25 mL of THF. The resulting light yellow solution was warmed to room temperature and stirred for 1 hour. After cooling to -78° C., a solution of 5.66 g (20.0 mmol) 1-bromo-4-iodobenzene and 300 mg (0.26 mmol) of tetrakis(triphenylphosphine)palladium in 20 mL of THF was added over the course of 15 minutes. After an additional 20 min, the cooling bath was removed, the reaction stirred at room temperature for 16 hours and then quenched with 50 mL of 2M hydrochloric acid. The mixture was extracted thrice with ether, the extracts combined, washed once with saturated sodium bicarbonate solution and once with 10% sodium thiosulfate. The organic extract was dried (MgSO4) and evaporated. The crude product was purified by flash chromatography on silica gel (5×25 cm column, hexanes as elutent) to give 4.05 g (72%) of title compound as a white solid, mp 121°-123° C.

Workup

  1. temperatureThe resulting light yellow solution was warmed to room temperature
  2. stirringstirred for 1 hour
  3. temperatureAfter cooling to -78° C.
  4. waitAfter an additional 20 min
  5. customthe cooling bath was removed
  6. stirringthe reaction stirred at room temperature for 16 hours
  7. customquenched with 50 mL of 2M hydrochloric acid
  8. extractionThe mixture was extracted thrice with ether
  9. washwashed once with saturated sodium bicarbonate solution and once with 10% sodium thiosulfate
  10. extractionThe organic extract
  11. dry with materialwas dried (MgSO4)
  12. customevaporated
  13. customThe crude product was purified by flash chromatography on silica gel (5×25 cm column, hexanes as elutent)

Sources & evidence

ORD record
ord-86abbecd9bb644e0ab796f89beda5683
Source dataset
uspto-grants-1995_11
Patent number
US05470845

Reaction notes

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