Triethylamine → 2-Cyano-4-methylpyridine

HRID 1858012Notes

Reaction equation

HRID 1858012 reaction equation
C(N(CC)CC)C.C[Si]([C:12]#[N:13])(C)C.[CH3:14][C:15]1[CH:20]=[CH:19][N+:18]([O-])=[CH:17][CH:16]=1.C(=O)(O)[O-].[Na+]>C(Cl)Cl.C(#N)C>[CH3:14][C:15]1[CH:20]=[CH:19][N:18]=[C:17]([C:12]#[N:13])[CH:16]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 138574-Picoline N-oxideHCID 82115Trimethylsilyl cyanideHCID 516892Sodium Bicarbonate

Product 1

HCID 887392-Cyano-4-methylpyridineYield 64.6%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

Triethylamine (13.4 mL, 91.9 mmol) and trimethylsilyl cyanide (25 mL, 187.5 mmol) were added sequentially to a solution comprising 4-methylpyridine N-oxide (5 g, 45.8 mmol) and acetonitrile (20 mL). The mixture was heated at reflux for 24 hours, cooled and diluted with methylene chloride (150 mL). Saturated sodium bicarbonate solution (100 mL) was added slowly to the mixture and then the aqueous layer was separated and extracted with methylene chloride (100 mL). The combined organic layers were washed with water (2×150 mL), dried (MgSO4) and concentrated under reduced pressure. The residue was crystallized from ethyl acetate/hexanes to provide 4-methylpyridine-2-carbonitrile (3.5 g, 29.6 mmol) as a dark solid, 1H-NMR (300 Mhz, DMSO-d6): 2.4 (s, 3H), 7.6 (d, 1H, J=5 Hz), 7.8 (s, 1H), 8.6 (d, 1H, J=5 Hz), MS (ESI), Calculated for C7H6N2 : 228.24, Found (MH+): 119.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 24 hours
  3. temperaturecooled
  4. customthe aqueous layer was separated
  5. extractionextracted with methylene chloride (100 mL)
  6. washThe combined organic layers were washed with water (2×150 mL)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was crystallized from ethyl acetate/hexanes

Sources & evidence

ORD record
ord-120a5b466867446387b823a3842b9710
Source dataset
uspto-grants-2000_11
Patent number
US06150379

Reaction notes

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