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

Temperature

-20 °C

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 thricefused zinc chloride. 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) of 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.

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. dry with materialwas dried (MgSO4)
11. customevaporated
12. distillationThe crude product (11.3 g) was purified by distillation (bp 93°-95° C. at 0.5 Torr)

ORD record

ord-d617cd918b464deabe1c3fe33495ba34

Source dataset

uspto-grants-1992_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05157027