Benzoyl Peroxide → 2-Cyano-5-hydroxymethylpyridine

HRID 2246383Notes

Reaction equation

HRID 2246383 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]#[N:9])=[N:6][CH:7]=1.BrN1C(=[O:16])CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.C(=O)([O-])[O-].[Ca+2]>ClC(Cl)(Cl)Cl.O>[OH:16][CH2:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]#[N:9])=[N:6][CH:7]=1

Participants

7

Reactant 4

HCID 7187Benzoyl PeroxideHCID 10112Calcium CarbonateHCID 67184N-bromobutanimideHCID 741835-Methylpicolinonitrile

Product 1

HCID 122519662-Cyano-5-hydroxymethylpyridine

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

The compound of Example 4A (13 g, 110 mmol) is dissolved in 400 ml tetrachloro-methane, and 29.4 g (165 mmol) N-bromosuccinimide and 0.4 g (1.6 mmol) dibenzoylperoxide are added. The reaction mixture is refluxed for three hours, cooled down to room temperature and filtered. The solution is washed with aqueous sodium thiosulfate, dried over magnesium sulfate, and the solvent is removed in vacuo. The residue is dissolved in 200 ml dioxane and 200 ml water, calciumcarbonate (44 g, 440 mmol) is added, and the mixture is stirred at reflux for 2 hours. After cooling down to room temperature, the mixture is filtered, and dichloromethane is added. After phase separation, the organic phase is dried over magnesium sulfate, and the solvent is removed in vacuo. The product is purified by chromatography (silica, eluent cyclohexane/ethyl acetate 2:1).

Workup

  1. temperatureThe reaction mixture is refluxed for three hours
  2. filtrationfiltered
  3. washThe solution is washed with aqueous sodium thiosulfate
  4. dry with materialdried over magnesium sulfate
  5. customthe solvent is removed in vacuo
  6. dissolutionThe residue is dissolved in 200 ml dioxane
  7. temperatureat reflux for 2 hours
  8. temperatureAfter cooling down to room temperature
  9. filtrationthe mixture is filtered
  10. additiondichloromethane is added
  11. customAfter phase separation
  12. dry with materialthe organic phase is dried over magnesium sulfate
  13. customthe solvent is removed in vacuo
  14. customThe product is purified by chromatography (silica, eluent cyclohexane/ethyl acetate 2:1)

Sources & evidence

ORD record
ord-668dceca931e46a59943d42ca568fca4
Source dataset
uspto-grants-2010_03
Patent number
US07687510B2

Reaction notes

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