p-Toluenesulfonic acid → Allyl 3-fluoro-5-nitrobenzoate

HRID 1392032Notes

Reaction equation

HRID 1392032 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(S(O)(=O)=O)=C[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 6101p-Toluenesulfonic acidHCID 7858Allyl AlcoholHCID 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), p-toluene-sulfonic acid (1.54 g, 8.1 mM), and allyl alcohol (50 ml) were heated to reflux, passing the distillate through 3a 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): δ 4.89 (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-afa0eba468e94d989717da232a40e5ee
Source dataset
uspto-grants-2008_03
Patent number
US07342005B2

Reaction notes

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