Phosphorus pentachloride → 2-Chloro-4,6-dimethyl-3-pyridinecarbonitrile

HRID 1921332Notes

Reaction equation

HRID 1921332 reaction equation
[C:1]([C:3]1[C:4](O)=[N:5][C:6]([CH3:10])=[CH:7][C:8]=1[CH3:9])#[N:2].P(Cl)(Cl)(Cl)(Cl)[Cl:13].C(=O)(O)[O-].[Na+]>>[Cl:13][C:4]1[C:3]([C:1]#[N:2])=[C:8]([CH3:9])[CH:7]=[C:6]([CH3:10])[N:5]=1

Participants

4

Reactant 3

HCID 24819Phosphorus pentachlorideHCID 516892Sodium BicarbonateHCID 178425241HCID 178425241, compound

Product 1

HCID 2232612-Chloro-4,6-dimethyl-3-pyridinecarbonitrileYield 94%

Conditions

Temperature
120 °C

Procedure

A stirred mixture of 3-cyano-4,6-dimethyl-2-hydroxypyridine (4.35 g, 29.39 mmol) and phosphorous pentachloride (6.92 g, 33.21 mmol) is heated to 120° C. The reaction mixture becomes clear and is stirred for an additional 1 hr. It is then poured onto ice/water (250 mL) and allowed to stand for 30 min. The solution is neutralized with sodium bicarbonate (pH 6) and extracted with dichloromethane (400 mL). The separated organic layer is dried, filtered and concentrated to yield 2-chloro-3-cyano-4,6-dimethylpyridine (4.60 g, 94% yield) as a tan solid containing ca 15% impurity. LC/MS: MS m/e=167/169 (M+H); RT 2.98 min; NMR (CDCl3, δ ppm) 7.08 (1H, s), 2.57 (3H, s), 2.55 (3H, s).

Workup

  1. additionIt is then poured onto ice/water (250 mL)
  2. waitto stand for 30 min
  3. extractionextracted with dichloromethane (400 mL)
  4. customThe separated organic layer is dried
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-c39b464b35684e3fb30f0b7cbf8cf361
Source dataset
uspto-grants-2012_05
Patent number
US08173682B2

Reaction notes

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