Benzoyl Peroxide → 4-Fluoro-3-phenoxybenzaldehyde

HRID 1666897Notes

Reaction equation

HRID 1666897 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[O:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.BrN1C(=[O:22])CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.C[N+]1([O-])CCOCC1>C(Cl)(Cl)(Cl)Cl>[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[O:22])=[CH:4][C:3]=1[O:9][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1

Participants

6

Reactant 4

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 82029Methyl morpholine oxideHCID 142572981-Fluoro-4-methyl-2-phenoxybenzene

Product 1

HCID 1100684-Fluoro-3-phenoxybenzaldehydeYield 8.5%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
0 °C

Procedure

Combine 4-fluoro-1-methyl-3-phenoxybenzene (2.43 g, 12.0 mmol), N-bromosuccinimide (4.92 g, 27.6 mmol), benzoyl peroxide (408 mg, 1.68 mmol), and carbon tetrachloride (55 mL). Heat the mixture at reflux temperature for 6.5 h and cool to 0° C. for 64 h. Filter the solids and concentrate the filtrate. Dissolve the residue in chloroform and wash with ice cold sodium carbonate solution. Dry the chloroform solution over sodium sulfate, filter and concentrate under reduced pressure. Dissolve the residue in acetonitrile (50 mL) and add 4-methylmorpholine-4-oxide (4.6 g, 39.1 mmol) and powdered 4 Å sieves (200 mg). Stir at ambient temperature for 20 h, filter and concentrate. Purify by silica gel chromatography (5%, 30% ethyl acetate/hexanes) to give 220 mg (8%) of the title compound: MS (m/e): 216 (M+).

Workup

  1. temperatureHeat the mixture
  2. temperatureat reflux temperature for 6.5 h
  3. filtrationFilter the solids
  4. concentrationconcentrate the filtrate
  5. dissolutionDissolve the residue in chloroform
  6. washwash with ice cold sodium carbonate solution
  7. dry with materialDry the chloroform solution over sodium sulfate
  8. filtrationfilter
  9. concentrationconcentrate under reduced pressure
  10. dissolutionDissolve the residue in acetonitrile (50 mL)
  11. filtrationfilter
  12. concentrationconcentrate
  13. customPurify by silica gel chromatography (5%, 30% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-e42d67a88943494da449cce1208df126
Source dataset
uspto-grants-2011_10
Patent number
US08044090B2

Reaction notes

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