Azobisisobutyronitrile → 3-(6-Bromo-3-bromomethyl-2-fluoro-phenoxy)-5-chloro-benzonitrile

HRID 1875067Notes

Reaction equation

HRID 1875067 reaction equation
[Br:1][C:2]1[C:7]([O:8][C:9]2[CH:10]=[C:11]([CH:14]=[C:15]([Cl:17])[CH:16]=2)[C:12]#[N:13])=[C:6]([F:18])[C:5]([CH3:19])=[CH:4][CH:3]=1.C1C(=O)N([Br:27])C(=O)C1.CC(N=NC(C#N)(C)C)(C#N)C.CCOC(C)=O>C(Cl)(Cl)(Cl)Cl.CCCCCC>[Br:1][C:2]1[C:7]([O:8][C:9]2[CH:10]=[C:11]([CH:14]=[C:15]([Cl:17])[CH:16]=2)[C:12]#[N:13])=[C:6]([F:18])[C:5]([CH2:19][Br:27])=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 684846323-[(6-Bromo-2-fluoro-3-methylphenyl)oxy]-5-chlorobenzonitrile

Product 1

HCID 669997373-(6-Bromo-3-bromomethyl-2-fluoro-phenoxy)-5-chloro-benzonitrileYield 32.3%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 8058HexaneSolvent

Procedure

A mixture of 3-[(6-bromo-2-fluoro-3-methylphenyl)oxy]-5-chlorobenzonitrile (3.39 g, 9.95 mmol), NBS (1.949 g, 10.95 mmol) and AIBN (0.082 g, 0.498 mmol) in carbon tetrachloride (45 ml) was heated at reflux overnight. The reaction mixture was filtered through Celite and the filtrate was evaporated to dryness. Chromatography of the residue (EtOAc:hexane) gave 3-{[6-bromo-3-(bromomethyl)-2-fluorophenyl]oxy}-5-chlorobenzonitrile (1.35 g, 32.3% yield) as a colorless oil which crystallized to a white solid. 1H NMR (400 MHz, chloroform-d) δ ppm 7.44 (dd, 1H), 7.34 (s, 1H), 7.19-7.27 (m, 1H), 7.10-7.15 (m, 1H), 6.97 (s, 1H), 4.45 (s, 2H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. filtrationThe reaction mixture was filtered through Celite
  4. customthe filtrate was evaporated to dryness

Sources & evidence

ORD record
ord-0bd2f3a979ba46fd94d34f44de5f2a9a
Source dataset
uspto-grants-2012_11
Patent number
US08304419B2

Reaction notes

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