tert-Butyl methyl ether → 1-Chloro-3-fluoro-5-nitrobenzene

HRID 522799Notes

Reaction equation

HRID 522799 reaction equation
B1([O-])OO1.[OH2:5].[OH2:6].O.O.[Na+].[Cl:10][C:11]1[CH:12]=[C:13]([CH:15]=[C:16]([F:18])[CH:17]=1)[NH2:14].CC(OC)(C)C>C(O)(=O)C>[Cl:10][C:11]1[CH:12]=[C:13]([N+:14]([O-:6])=[O:5])[CH:15]=[C:16]([F:18])[CH:17]=1

Participants

5

Reactant 3

HCID 15413tert-Butyl methyl etherHCID 27348383-Chloro-5-fluoroanilineHCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrate

Product 1

HCID 233688911-Chloro-3-fluoro-5-nitrobenzeneYield 18.2%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Conditions

Temperature
55 °C

Procedure

Sodium perborate tetrahydrate (7.69 g, 50.0 mmol) was suspended in 30 mL of acetic acid, and this suspension was warmed to 55° C. 3-Chloro-5-fluoroaniline (1.46 g, 10 mmol) was dissolved in 20 mL of acetic acid and added within one hour. The reaction was stirred for 1 hour at 55° C. and then cooled to room temperature. 300 mL of TBME was added, and the reaction mixture was filtered. The organic layer was washed with brine, followed by 20 mL of aqueous Na2S2O3, followed by brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure to give a residue, which was purified by column chromatography (40 g SiO2; cyclohexane) to yield the title compound as a solid (320 mg, 18%). 1H-NMR (400 MHz; DMSO-d6): 8.20 (s, 1H), 8.18 (d, 1H), 8.07 (d, 1H).

Workup

  1. additionadded within one hour
  2. temperaturecooled to room temperature
  3. filtrationthe reaction mixture was filtered
  4. washThe organic layer was washed with brine
  5. dry with materialThe organic layer was dried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customto give a residue, which
  8. customwas purified by column chromatography (40 g SiO2; cyclohexane)

Sources & evidence

ORD record
ord-2b5e73f8363b4225af4525025e69b8b4
Source dataset
uspto-grants-2016_05
Patent number
US09334271B2

Reaction notes

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