1-Bromo-4-iodobenzene → 4'-Bromo-2-methyl-1,1'-biphenyl

HRID 1029845Notes

Reaction equation

HRID 1029845 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[Mg]Br.[Br:10][C:11]1[CH:16]=[CH:15][C:14](I)=[CH:13][CH:12]=1>O1CCCC1.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:10][C:11]1[CH:16]=[CH:15][C:14]([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2[CH3:1])=[CH:13][CH:12]=1

Participants

5

Reactant 2

HCID 115221-Bromo-4-iodobenzeneHCID 178424303HCID 178424303, compound

Product 1

HCID 152058764'-Bromo-2-methyl-1,1'-biphenylYield 82%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-20 °C

Procedure

A stirred solution of 21.0 mL of (2-methylphenyl)magnesium bromide (42.0 mmol, 2.0M in diethyl ether) was evaporated in situ at room temperature. The syrupy residue was redissolved in 50 mL of THF and cooled to -20° C. under argon. To this solution was added a solution of 6.84 g (50.0 mmol) of thrice-fused zinc chloride in 50 mL of tetrahydrofuran (THF). The resulting thick white slurry was warmed to room temperature and stirred for 1 hour. After cooling to -78° C., a solution of 11.32 g (40.0 mmol) 1-bromo-4-iodobenzene and 500 mg (0.4 mmol) of tetrakis(triphenylphosphine)palladium in 50 mL of THF was added over the course of thirty minutes. After an additional 20 minutes, the cooling bath was removed, the reaction stirred at room temperature for 2 hours and then quenched with 100 mL of 1M hydrochloric acid. The mixture was extracted twice with hexanes, 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 (11.3 g) was purified by distillation (bp 93°-95° C. at 0.5 Torr) to give 8.06 g (82%) of title compound as a colorless oil.

Workup

  1. temperatureThe resulting thick white slurry was warmed to room temperature
  2. temperatureAfter cooling to -78° C.
  3. waitAfter an additional 20 minutes
  4. customthe cooling bath was removed
  5. stirringthe reaction stirred at room temperature for 2 hours
  6. customquenched with 100 mL of 1M hydrochloric acid
  7. extractionThe mixture was extracted twice with hexanes
  8. washwashed once with saturated sodium bicarbonate solution and once with 10% sodium thiosulfate
  9. extractionThe organic extract
  10. customwas dried (MgSo4)
  11. customevaporated
  12. distillationThe crude product (11.3 g) was purified by distillation (bp 93°-95° C. at 0.5 Torr)

Sources & evidence

ORD record
ord-a74c81f3dd264d5f807b168202d3b98f
Source dataset
uspto-grants-1992_04
Patent number
US05103036

Reaction notes

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