4-Chloroanisole → 4-o-Tolylanisole

In the drybox, 54.0 mg (0.303 mm) of (Me3C)2PH(S) (from Experiment 18), 83.4 mg (0.303 mm) of Ni(COD)2 and 10.0 mL of THF were loaded into a reactor (20 mL) equipped with a magnetic stir bar. The resulting mixture was stirred at room temperatureover a period of 10 min. After addition of 1.43 g (10.0 mm) of 4-chloroanisol, the resulting mixture was stirred for 5 min until the catalytic reaction was initiated by dropwise addition of 15 mL (15.0 mm, 1.0 M in THF) of o-tolylmagnesium chloride at room temperature over a period of 5 min. The resulting mixture was stirred at room temperature over 12 h before the reaction was quenched with 10.0 mL of H2O, and the mixture was diluted with 300 mL of Et2O. After separation of organic and aqueous phases, the organic phase was washed with 2×100 mL of H2O, and 100 mL of brine, then dried over mgSO4, filtered and concentrated by rotary evaporation. The crude product was purified by column chromatography on silica gel (100:1-hexane:methyl t-butyl ether) to afford 0.90 g (45% yield) of 4-(o-tolyl)anisole.

1. custom(20 mL) equipped with a magnetic stir bar
2. stirringthe resulting mixture was stirred for 5 min until the catalytic reaction
3. stirringThe resulting mixture was stirred at room temperature over 12 h before the reaction
4. customwas quenched with 10.0 mL of H2O
5. additionthe mixture was diluted with 300 mL of Et2O
6. customAfter separation of organic and aqueous phases
7. washthe organic phase was washed with 2×100 mL of H2O, and 100 mL of brine
8. customdried over mgSO4
9. filtrationfiltered
10. concentrationconcentrated by rotary evaporation
11. customThe crude product was purified by column chromatography on silica gel (100:1-hexane:methyl t-butyl ether)

ORD record

ord-e896eca009ca4604a7c0a90f0602fb07

Source dataset

uspto-grants-2004_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06762330B2