Hydrogen Peroxide → 4-Propylpicolinonitrile

HRID 901451

Reaction equation

HRID 901451 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][N:7]=[CH:6][CH:5]=1)[CH2:2][CH3:3].OO.C[Si]([C:16]#[N:17])(C)C.CN(C)C(Cl)=O>C(=O)([O-])[O-].[K+].[K+]>[CH2:1]([C:4]1[CH:9]=[CH:8][N:7]=[C:6]([C:16]#[N:17])[CH:5]=1)[CH2:2][CH3:3]

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 6598Dimethylcarbamoyl ChlorideHCID 707384-PropylpyridineHCID 82115Trimethylsilyl cyanide

Product 1

HCID 230032234-PropylpicolinonitrileYield 93%

Reagents, catalysts & solvents 1

HCID 11430Potassium CarbonateSolvent

Procedure

To 4-propylpyridine (TCI) (2.5 g, 20 mmol), 30% hydrogen peroxide (2.4 g) was added and refluxed overnight. The solvent was removed and the resulting residue was taken in DCM (30 mL). Trimethylsilyl cyanide (2.6 g, 26 mmol) was added to the above solution followed by dimethyl carbamyl chloride (2.8 g, 26 mmol) and left stirred at room temperature overnight. Potassium carbonate (10%, 100 mL) was added. The organic layer was separated, dried over sodium sulfate and then concentrated to obtain 4-propyl-2-cyanopyridine (2.5 g, 93%). It was then refluxed in hydrochloric acid (6N, 60 mL) for overnight. The 4-propylpyridinecarboxylic acid 10b (R9=n-Propyl) was obtained after crystallization from acetonitrile (2.0 g, 71%): MS (ESPOS): 166 [M+H]+; 1H NMR (300 MHz, CD3OD) δ 8.75 (dd, J=9.0, 3.0, 1), 8.42 (s, 1), 8.08 (dd, J=9.0, 3.0, 1), 3.00 (t, J=7.5, 2), 1.82 (m, 2), 1.05 (t, J=7.2, 3).

Workup

  1. temperaturerefluxed overnight
  2. customThe solvent was removed
  3. waitleft
  4. customThe organic layer was separated
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-815de67fa2954e29bd3f3cd80a214e20
Source dataset
uspto-grants-2008_04
Patent number
US07361743B2

Linked notes

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