N-bromobutanimide → 2-(Bromomethyl)-6-fluoropyridine

HRID 545542Notes

Reaction equation

HRID 545542 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[N:3]=1.[Br:9]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.N(C1(C#N)CCCCC1)=NC1(C#N)CCCCC1>[Br:9][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[N:3]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 960902-Fluoro-6-methylpyridine

Product 1

HCID 139852182-(Bromomethyl)-6-fluoropyridineYield 37%

Reagents, catalysts & solvents 2

HCID 749781,1'-Azobis(cyclohexanecarbonitrile)CatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

Combine 2-methyl-6-fluoro-pyridine (19.6 g, 176 mmol), 1,1′-azobis-(cyclohexane-carbonitrile) (0.431 g, 1.77 mmol), and freshly recystallized N-bromo-succinimide (32.96 g, 185 mmol) in carbon tetrachloride (200 mL) and stir in a 1000 mL flask while radiating with UV light for 18 h. Allow to cool, then filter to remove succinimide and wash with dilute Na2S2O3 solution. Dry over Na2SO4, filter and evaporate to give an amber oil. Purify by silica gel chromatography, eluting with 0-30% EtOAc/hexanes to obtain 12.3 g (37%) of a clear oil. MS 100% (m/e) 190 (EI); 1H NMR (DMSO, 400 MHz): δ 8.03-7.95 (m, 1H), 8.03-7.95 (m, 1H), 7.48 (dd, 1H, J=7.5, 2.6 Hz), 7.11 (dd, 1H, J=7.9, 2.6 Hz), 4.63 (s, 2H).

Workup

  1. temperatureto cool
  2. filtrationfilter
  3. customto remove succinimide
  4. washwash with dilute Na2S2O3 solution
  5. dry with materialDry over Na2SO4
  6. filtrationfilter
  7. customevaporate
  8. customto give an amber oil
  9. customPurify by silica gel chromatography
  10. washeluting with 0-30% EtOAc/hexanes

Sources & evidence

ORD record
ord-4354dfce5bf2416e8d7b6007c9899f3b
Source dataset
uspto-grants-2011_05
Patent number
US07935722B2

Reaction notes

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