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

HRID 2184212Notes

Reaction equation

HRID 2184212 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 MHz, CDCl3) 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-33d2ad0d419e49da81cc136fad2fddab
Source dataset
uspto-grants-2005_05
Patent number
US06900231B2

Reaction notes

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