Benzoyl Peroxide → 4-Cyano-3-fluorobenzyl bromide

HRID 1935407Notes

Reaction equation

HRID 1935407 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH3:9])=[CH:5][C:4]=1[F:10])#[N:2].[Br:11]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][Br:11])=[CH:5][C:4]=1[F:10])#[N:2]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimide2×HCID 27784432-Fluoro-4-methylbenzonitrile

Product 1

HCID 27784664-Cyano-3-fluorobenzyl bromide

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of the product from Step A (22.2 g, 165 mmol) in 220 mL of carbontetrachloride was added N-bromosuccinimide (29.2 g, 164 mmol) and benzoylperoxide (1.1 g). The reaction was heated to reflux for 30 minutes, then cooled to room temperature. The solution was concentrated in vacuo to one-third the original volume, poured into EtOAc, washed with water, sat. aq. NaHCO3, and brine, then dried (Na2SO4), filtered, and concentrated in vacuo to provide the crude product. Analysis by 1H NMR indicated only partial conversion, so the crude material was resubjected to the same reaction conditions for 2.5 hours, using 18 g (102 mmol) of N-bromosuccinimide. After workup, the crude material was purified by silica gel chromatography (0-10% EtOAc/hexane) to provide the desired product.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux for 30 minutes
  3. concentrationThe solution was concentrated in vacuo to one-third the original volume
  4. additionpoured into EtOAc
  5. washwashed with water, sat. aq. NaHCO3, and brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto provide the crude product
  10. customAfter workup, the crude material was purified by silica gel chromatography (0-10% EtOAc/hexane)

Sources & evidence

ORD record
ord-7dc71765fb1945ff92f5507dde82a28f
Source dataset
uspto-grants-2002_05
Patent number
US06387903B1

Reaction notes

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