Benzyl Bromide → 4-Benzyloxy-2-fluoro-1-nitrobenzene

HRID 601276Notes

Reaction equation

HRID 601276 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([OH:11])[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].[CH2:12](Br)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O>[CH2:12]([O:11][C:4]1[CH:5]=[CH:6][C:7]([N+:8]([O-:10])=[O:9])=[C:2]([F:1])[CH:3]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 3

HCID 7498Benzyl BromideHCID 10796Cesium carbonateHCID 5209483-Fluoro-4-nitrophenol

Product 1

HCID 221807044-Benzyloxy-2-fluoro-1-nitrobenzeneYield 94.8%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent

Procedure

3-Fluoro-4-nitro-phenol (10 g, 0.064 mol) was reacted with benzyl bromide (8.3 ml, 0.070 mol), cesium carbonate (22.7 g, 0.07 mol), and tetrabutyl ammonium iodide (0.05 g) in N,N-dimethylformamide (100 mL) at 25° C. for 18 hr. The reaction mixture was poured into distilled water (500 mL) and stirred for 10 minutes. The reaction mixture was extracted with ethyl acetate (3×200 mL). The combined organic extracts were washed with brine, dried over anhydrous sodium sulfate, filtered and solvent removed under reduced pressure to give the title compound as a light yellow solid (15 g). 1H NMR (300 MHz, DMSO-d6) δ ppm 5.27 (s, 2 H) 7.06 (dd, J=9.56, 2.57 Hz, 1 H) 7.29 (dd, J=13.60, 2.57 Hz, 1 H) 7.44 (m, 5 H) 8.17 (t, J=9.19 Hz, 1 H). ESI m/z (M+H)+: 248

Workup

  1. additionThe reaction mixture was poured
  2. distillationinto distilled water (500 mL)
  3. extractionThe reaction mixture was extracted with ethyl acetate (3×200 mL)
  4. washThe combined organic extracts were washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customsolvent removed under reduced pressure

Sources & evidence

ORD record
ord-f3739d4c3ecd4f06a0397744e9220fbe
Source dataset
uspto-grants-2011_03
Patent number
US07902203B2

Reaction notes

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