Allyl Alcohol → Allyl 3-fluoro-5-nitrobenzoate

HRID 2260788Notes

Reaction equation

HRID 2260788 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5]([OH:7])=[O:6].[C:14]1(C)[CH:19]=CC=C(S(O)(=O)=O)[CH:15]=1.C(O)C=C>C(N(CC)CC)C>[F:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)[C:5]([O:7][CH2:19][CH:14]=[CH2:15])=[O:6]

Participants

5

Reactant 3

HCID 7858Allyl AlcoholHCID 105362m-Toluenesulfonic acidHCID 27590473-Fluoro-5-nitrobenzoic acid

Product 1

HCID 22168638Allyl 3-fluoro-5-nitrobenzoate

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

3-Fluoro-5-nitrobenzoic acid (3 g, 16.2 mM), m-toluenesulfonic acid (1.54 g, 8.1 mM), and allyl alcohol (50 ml) were heated to reflux, passing the distillate through 3å molecular sieves, for 16 hours. After cooling, the mixture was neutralised with triethylamine, and solvent removed. The residue was dissolved in ethyl acetate, washed with 2M hydrochloric acid, aqueous NaHCO3, and brine, and dried over MgSO4. Crude product was purified by chromatography on silica, using a gradient elution from dichloromethane to ethyl acetate/dichloromethane (3:1), to give allyl 3-fluoro-5-nitrobenzoate. Nmr (CDCl3): δ4.89 (dt, 2H); 5.33-5.49 (m, 2H); 5.95-6.15 (m, 1H); 8.11 (m, 2H); 8.70 (t, 1H).

Workup

  1. temperatureto reflux
  2. temperatureAfter cooling
  3. customremoved
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwashed with 2M hydrochloric acid, aqueous NaHCO3, and brine
  6. dry with materialdried over MgSO4
  7. customCrude product was purified by chromatography on silica
  8. washa gradient elution from dichloromethane to ethyl acetate/dichloromethane (3:1)

Sources & evidence

ORD record
ord-ae10142f09344d5f944e20053b9d9cf1
Source dataset
uspto-grants-1995_12
Patent number
US05478820

Reaction notes

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