Triethylamine → 3,5-Dibromopicolinonitrile

HRID 2364547Notes

Reaction equation

HRID 2364547 reaction equation
[Br:1][C:2]1[CH:3]=[N+:4]([O-])[CH:5]=[C:6]([Br:8])[CH:7]=1.[CH2:10]([N:12](CC)CC)C.C[Si](C#N)(C)C>C(#N)C.ClCCl.C(=O)([O-])[O-].[Na+].[Na+].O>[Br:1][C:2]1[C:3]([C:10]#[N:12])=[N:4][CH:5]=[C:6]([Br:8])[CH:7]=1

Participants

8

Reactant 3

HCID 8471TriethylamineHCID 82115Trimethylsilyl cyanideHCID 6200033,5-Dibromopyridine 1-oxide

Product 1

HCID 123612023,5-DibromopicolinonitrileYield 73.2%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolventHCID 10340Sodium CarbonateSolvent

Procedure

3,5-dibromopyridine 1-oxide (25.09g, 0.099 mol) was dissolved in acetonitrile (200 mL) and triethylamine (28 mL, 0.198 mol) and trimethylsilylcyanide (40 mL, 0.297 mol) were added. The reaction was stirred 16 hours and then diluted with dichloromethane, aqueous sodium carbonate, water, and then filtered through Celite eluting with dichloromethane. The mixture was extracted with dichloromethane and purified by silica gel chromatography (3:2 hexanes:ethyl acetate gradient elution) to afford 3,5-dibromo-2-pyridinecarbonitrile (18.98 g, 73% yield) as a tan solid. 1H NMR (CDCl3) δ 8.68 (d, J=2 Hz, 1 H), 8.20 (d, J=2 Hz, 1 H); MS m/z 262 M+1).

Workup

  1. filtrationfiltered through Celite
  2. washeluting with dichloromethane
  3. extractionThe mixture was extracted with dichloromethane
  4. custompurified by silica gel chromatography (3:2 hexanes:ethyl acetate gradient elution)

Sources & evidence

ORD record
ord-eff1a76bb8184ea4809e813b0a159886
Source dataset
uspto-grants-2014_04
Patent number
US08691991B2

Reaction notes

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