Water → 1-Chloro-2-fluoro-4-(2-nitro-vinyl)-benzene

HRID 19776Notes

Reaction equation

HRID 19776 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][C:3]=1[F:10].C([O-])(=O)C.[NH4+].[N+:16]([CH3:19])([O-:18])=[O:17].O>C(O)(=O)C>[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[CH:19][N+:16]([O-:18])=[O:17])=[CH:4][C:3]=1[F:10]

Participants

6

Reactant 4

HCID 962WaterHCID 6375NitromethaneHCID 517165Ammonium AcetateHCID 27249854-Chloro-3-Fluorobenzaldehyde

Product 1

HCID 668017121-Chloro-2-fluoro-4-(2-nitro-vinyl)-benzeneYield 66%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

4-Chloro-3-fluorobenzaldehyde (13 g, 82 mmol) and ammonium acetate (14.6 g, 189 mmol) were dissolved in acetic acid (150 ml) and nitromethane (12.6 ml, 234 mmol) was added. The solution was heated to reflux for 1.5 h. After cooling to RT water (120 ml) was added. A solid precipitated. The reaction was extracted three times with methylene chloride. The combined organic layers were washed with water and sat. aq. NaCl solution, dried over magnesium sulfate, filtered and the solvent was removed in vacuo. The residue was purified by flash column chromatography (Ethyl acetate/cyclohexane:1/4). The crude product was suspended in heptane, filtered and dried to yield 1-chloro-2-fluoro-4-(2-nitro-vinyl)-benzene (10.9 g, 66%) as a light yellow solid. 1H NMR (CDCl3, 300 MHz): δ 7.29 (d, J=7.8 Hz, 1H), 7.33 (d, J=9.3 Hz, 1H), 7.50 (t, J=7.5H7, 1H), 7.54 (d, J=13.6 Hz, 1H), 7.92 (d, J=13.6 Hz, 1H).

Workup

  1. temperatureThe solution was heated
  2. temperatureto reflux for 1.5 h
  3. additionwas added
  4. customA solid precipitated
  5. extractionThe reaction was extracted three times with methylene chloride
  6. washThe combined organic layers were washed with water and sat. aq. NaCl solution
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customthe solvent was removed in vacuo
  10. customThe residue was purified by flash column chromatography (Ethyl acetate/cyclohexane:1/4)
  11. filtrationfiltered
  12. customdried

Sources & evidence

ORD record
ord-70e359c85a384e3e9b73af537a6e2a11
Source dataset
uspto-grants-2010_06
Patent number
US07745477B2

Reaction notes

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