Methanol → 2-(Hydroxymethyl)pyridine-4-carbonitrile

HRID 1161129Notes

Reaction equation

HRID 1161129 reaction equation
S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].[C:13](#[N:20])[C:14]1[CH:19]=[CH:18][N:17]=[CH:16][CH:15]=1.S(=O)(=O)(O)O.[OH-:26].[NH4+].[CH3:28]O>C(Cl)(Cl)Cl.O>[OH:26][CH2:28][C:16]1[CH:15]=[C:14]([CH:19]=[CH:18][N:17]=1)[C:13]#[N:20]

Participants

8

Reactant 5

HCID 887MethanolHCID 1118Sulfuric AcidHCID 75064-CyanopyridineHCID 14923Ammonium HydroxideHCID 62648Ammonium Persulfate

Product 1

HCID 132925992-(Hydroxymethyl)pyridine-4-carbonitrileYield 28%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

Add ammonium persulfate (70.1 g, 307 mmol) to a solution of isonicotinonitrile (16.00 g, 154 mmol) in methanol:water:sulfuric acid (275 mL:135 mL:11 mL). Heat solution to reflux. After 24 hours, pour reaction onto ice and neutralize with ammonium hydroxide (70 ml). Extract solution with chloroform (3×600 ml). Combine the organic layers, dry with sodium sulfate, filter, and concentrate under reduced pressure to give a residue. Purify the residue by flash chromatography eluting with acetone:dichloromethane (1:6) to yield the title compound as a white solid (5.86 g, 28%): 1H NMR (CDCl3) δ 3.17 (t, 1H), 4.84 (d, 1H), 7.45 (m, 1H), 7.58 (s, 1H), 8.74 (d, 1H).

Workup

  1. temperatureHeat solution to reflux
  2. additionpour
  3. customreaction onto ice
  4. dry with materialCombine the organic layers, dry with sodium sulfate
  5. filtrationfilter
  6. concentrationconcentrate under reduced pressure
  7. customto give a residue
  8. customPurify the residue by flash chromatography
  9. washeluting with acetone:dichloromethane (1:6)

Sources & evidence

ORD record
ord-1f05181792d74f31b66bf75b258090e6
Source dataset
uspto-grants-2010_10
Patent number
US07816523B2

Reaction notes

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