N-bromobutanimide → 2-(Bromomethyl)-1-fluoro-4-nitrobenzene

HRID 1257197Notes

Reaction equation

HRID 1257197 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[CH3:11].C1C(=O)N([Br:19])C(=O)C1>FC(F)(F)C1C=CC=CC=1.CC(N=NC(C#N)(C)C)(C#N)C>[Br:19][CH2:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[F:1]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 68001Benzene, 1-fluoro-2-methyl-4-nitro-

Product 1

HCID 103539672-(Bromomethyl)-1-fluoro-4-nitrobenzeneYield 50.8%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 7368(Trifluoromethyl)benzeneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 1-fluoro-2-methyl-4-nitrobenzene (2.5 g, 16.12 mmol) and NBS (3.16 g, 17.73 mmol) in trifluorotoluene (45 mL) was treated with AIBN (66 mg, 0.403 mmol) and heated at 80° C. overnight. The mixture was cooled to RT, the solids removed via filtration and the filtrate concentrated to dryness. The residue was dissolved in EtOAc, washed with water, then brine, dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (EtOAc/Hex) to afford 2-(bromomethyl)-1-fluoro-4-nitrobenzene (1.915 g, 50% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.53-8.52 (m, 1H), 8.28 (ddd, J=9.1, 4.4, 3.0 Hz, 1H), 7.55 (t, J=9.2 Hz, 1H), 4.80 (s, 2H).

Workup

  1. temperatureThe mixture was cooled to RT
  2. customthe solids removed via filtration
  3. concentrationthe filtrate concentrated to dryness
  4. dissolutionThe residue was dissolved in EtOAc
  5. washwashed with water
  6. dry with materialbrine, dried over Na2SO4
  7. concentrationconcentrated to dryness
  8. custompurified via silica gel chromatography (EtOAc/Hex)

Sources & evidence

ORD record
ord-2e7afb2dcb6f4bdebce907b428def65e
Source dataset
uspto-grants-2013_06
Patent number
US08461179B1

Reaction notes

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