Hydrochloric Acid → 2-Chloro-4-phenyl-6-(phenylsulfanyl)-3,5-pyridinedicarbonitrile

HRID 885660Notes

Reaction equation

HRID 885660 reaction equation
N(OCCC(C)C)=O.N[C:10]1[C:15]([C:16]#[N:17])=[C:14]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:13]([C:24]#[N:25])=[C:12]([S:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[N:11]=1.[ClH:33]>C(#N)C.[Cu](Cl)Cl>[Cl:33][C:10]1[C:15]([C:16]#[N:17])=[C:14]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:13]([C:24]#[N:25])=[C:12]([S:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[N:11]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 8053Isoamyl NitriteHCID 41651072-Amino-4-phenyl-6-phenylsulfanylpyridine-3,5-dicarbonitrile

Product 1

HCID 120183412-Chloro-4-phenyl-6-(phenylsulfanyl)-3,5-pyridinedicarbonitrile

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 6342AcetonitrileSolvent

Procedure

Under argon, 24.5 g (182 mmol) of anhydrous copper(II) chloride are suspended in 180 ml of acetonitrile, and 21.4 g (182 mmol) of isopentyl nitrite are then added dropwise. After 20 min of stirring at room temperature, 10 g (30.5 mmol) of 2-amino-4-phenyl-6-(phenylsulfanyl)-3,5-pyridinedicarbonitrile [Kambe et al., Synthesis, 531-533 (1981)] are added. The mixture is stirred at room temperature over the weekend. For work-up, 150 ml of 1 N hydrochloric acid are added to the mixture, the mixture is extracted 4× with dichloromethane and the organic phase is washed once with saturated sodium chloride solution, dried over magnesium sulfate and concentrated under reduced pressure. The residue is triturated with a little ethyl acetate and allowed to stand in a fridge for 1 hour. The crystals are filtered off with suction and washed with a little cold ethyl acetate and diethyl ether.

Workup

  1. stirringThe mixture is stirred at room temperature over the weekend
  2. extractionthe mixture is extracted 4× with dichloromethane
  3. washthe organic phase is washed once with saturated sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue is triturated with a little ethyl acetate
  7. waitto stand in a fridge for 1 hour
  8. filtrationThe crystals are filtered off with suction
  9. washwashed with a little cold ethyl acetate and diethyl ether

Sources & evidence

ORD record
ord-9519d7b7d15f45b2a55083ff36c8f0f4
Source dataset
uspto-grants-2012_08
Patent number
US08242281B2

Reaction notes

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