Allyl bromide → 2-(Allyloxy)-4-methyl-1-nitrobenzene

HRID 1060230Notes

Reaction equation

HRID 1060230 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([OH:8])[CH:7]=1.[CH2:12](Br)[CH:13]=[CH2:14].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([O:8][CH2:14][CH:13]=[CH2:12])[CH:7]=1

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 10796Cesium carbonateHCID 127886-Nitro-m-cresol

Product 1

HCID 135756662-(Allyloxy)-4-methyl-1-nitrobenzeneYield 95%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 5-methyl-2-nitrophenol (2.00 g, 13.1 mmol), allyl bromide (1.30 mL, 15.0 mmol), and cesium carbonate (5.5 g, 17 mmol) in DMF (100 mL) was stirred at ambient temperature. After 20 hrs the reaction was filtered, frit washed with methanol, and the filtrate evaporated in vacuo at 50° C. The residue was purified by flash column chromatography (4:1 then 2:1 hexane:ethyl acetate eluant) giving the title compound as a yellow oil (2.39 g, 95%) that crystallized after sitting 3 days at ambient temperature. 1H NMR (300 Mz, DCl3) δ 7.79 (d, 1H, J=8.2 Hz), 6.86 (s, 1H), 6.82 (m, 1H), 6.05 (ddt, 1H, J=17.3 Hz, 10.6 Hz, 5.0 Hz), 5.50 (ddd, 1H, J=17.3 Hz, 3.3 Hz, 1.7 Hz), 5.33 (ddd, 1H, J=10.6 Hz, 2.9 Hz, 1.5 Hz), 4.67 (dt, 2H, J=4,9 Hz, 1.6 Hz), 2.40 (s, 3H).

Workup

  1. filtrationAfter 20 hrs the reaction was filtered
  2. washfrit washed with methanol
  3. customthe filtrate evaporated in vacuo at 50° C
  4. customThe residue was purified by flash column chromatography (4:1

Sources & evidence

ORD record
ord-e937650471254c9ca85f73f03af6a602
Source dataset
uspto-grants-2003_02
Patent number
US06521663B2

Reaction notes

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