4-Chloroanisole → 4-Methoxybiphenyl

HRID 1596846Notes

Reaction equation

HRID 1596846 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.[C:10]1(B(O)O)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.[F-].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[C:10]1([C:2]2[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

6

Reactant 3

HCID 121674-ChloroanisoleHCID 25953Cesium fluorideHCID 66827Phenylboronic Acid

Product 1

HCID 119434-MethoxybiphenylYield 97%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

In the drybox, 9.6 mg (0.058 mmol) of (Me3C)2PH(O) from Experiment 2, 13.3 mg (0.0145 mmol) of Pd2(dba)3 and 3.0 mL of 1,4-dioxane were loaded into a reactor (20 mL) equipped with a magnetic stir bar. The resulting mixture was stirred at room temperature overnight. Next, 143.0 mg (1.0 mm) of 4-chloro-anisole, 182.9 mg (1.5 mm) of PhB(OH)2 and 456 mg (3.0 mmol) of CsF were added into the reactor. The resulting mixture was refluxed for 24 h. The reaction mixture was then cooled to room temperature, chromatographed on silicon gel using ethyl acetate/hexane (5% volume ratio) as eluant. The eluate was concentrated by rotary evaporation followed by high vacuum to yield 179 mg (97% yield) of 4-phenylanisole. It was >95% pure by 1H NMR and GC/MS. 1H NMR (500 MHz, CDCl3): δ 7.45 (m, 4H), 7.32 (m, 2H), 7.21 (m, 1H), 6.88 (d, J=8.72 Hz, 2H), 3.74 (s, 3H) ppm. 13C NMR (125 MHz, CDCl3): δ 159.2, 140.8, 133.8, 128.7, 128.1, 126.7, 126.6, 114.2, 55.3 ppm.

Workup

  1. custom(20 mL) equipped with a magnetic stir bar
  2. temperatureThe resulting mixture was refluxed for 24 h
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. customchromatographed on silicon gel
  5. concentrationThe eluate was concentrated by rotary evaporation

Sources & evidence

ORD record
ord-55ede6d1dc474a6ba15075232d54af18
Source dataset
uspto-grants-2001_09
Patent number
US06291722B1

Reaction notes

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