Azobisisobutyronitrile → 2-(Bromomethyl)-6-fluoropyridine
Reaction equation
C1C(=O)N([Br:8])C(=O)C1.[F:9][C:10]1[N:15]=[C:14]([CH3:16])[CH:13]=[CH:12][CH:11]=1.CC(N=NC(C#N)(C)C)(C#N)C.CCCCCC>CCOC(C)=O>[Br:8][CH2:16][C:14]1[CH:13]=[CH:12][CH:11]=[C:10]([F:9])[N:15]=1Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 65 °C
Procedure
Add NBS (35.6 g, 0.20 mole) to a solution of 6-fluoro-2-methylpyridine (20 mL, 0.19 mole) in EtOAc (400 mL) at room temperature. When the temperature reaches 45° C., add AIBN (400 mg, 2.4 mmol). Heat the mixture at 65° C. for 6 h, then cool to room temperature and add hexane (1 L). Remove the white precipitate by filtration and wash the solid with hexane/EtOAc (1:1). Wash the filtrate with small amounts of aqueous Na2S2O3, NaHCO3, and brine. Dry the organics (Na2SO4), filter, then remove most of the solvent under vacuum at room temperature. Transfer the remaining solution to a distillation set-up. Remove the remaining solvent by distilling at atmospheric pressure, followed by the unreacted starting material at 80 mm (bp ca 70° C.; 11.2 g) and then the title product at 1 mm (bp ca 75° C.; 12.1 g, 32%). NMR (300 MHz; CDCl3): 7.82 (1H; dd); 7.35 (1H; dd); 6.90 (1H; dd); 4.50 (2H; s).
Workup
- customreaches 45° C.
- temperaturecool to room temperature
- customRemove the white precipitate
- filtrationby filtration
- washwash the solid with hexane/EtOAc (1:1)
- washWash the filtrate with small amounts of aqueous Na2S2O3, NaHCO3, and brine
- dry with materialDry the organics (Na2SO4)
- filtrationfilter
- customremove most of the solvent under vacuum at room temperature
- customRemove the remaining solvent
- distillationby distilling at atmospheric pressure
Sources & evidence
- ORD record
- ord-965146ba5115477bbbd329ced55b5460
- Source dataset
- uspto-grants-2011_06
- Patent number
- US07968587B2
Reaction notes
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