Pivalic acid → 6-Tert-butyl-2-chloropyridine-3-carbonitrile

HRID 1961484Notes

Reaction equation

HRID 1961484 reaction equation
[Cl:1][C:2]1[N:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[C:10](O)(=O)[C:11](C)([CH3:13])[CH3:12].S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].[NH4+].[OH-]>OS(O)(=O)=O.O.[N+]([O-])([O-])=O.[Ag+]>[C:11]([C:8]1[CH:7]=[CH:6][C:3]([C:4]#[N:5])=[C:2]([Cl:1])[N:9]=1)([CH3:13])([CH3:12])[CH3:10]

Participants

8

Reactant 4

HCID 6417Pivalic acidHCID 14923Ammonium HydroxideHCID 62648Ammonium PersulfateHCID 810792-Chloronicotinonitrile

Product 1

HCID 532788766-Tert-butyl-2-chloropyridine-3-carbonitrileYield 38%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Procedure

2-Chloronicotinonitrile (2.1 g, 15.2 mmol), pivalic acid (7.7 g, 75.8 mmol) and silver nitrate (0.5 g, 3.0 mmol) were suspended in 10% aqueous H2SO4 (20 ml). Ammonium persulfate (6.9 g, 30.3 mmol) in H2O (40 ml) was added to the mixture. The mixture was stirred at r.t. for 36 h. NH4OH was added until pH=9. The product was extracted with EtOAc. The combined organic extracts were washed with water, dried (MgSO4), filtered and concentrated. Purification was done by flash chromatography (Pet. Ether/EtOAc 9:1) to give the title substance in 38% yield.

Workup

  1. extractionThe product was extracted with EtOAc
  2. washThe combined organic extracts were washed with water
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification
  7. customto give the title substance in 38% yield

Sources & evidence

ORD record
ord-46687e4c9cc04a01ae2a5dd3793662c8
Source dataset
uspto-grants-2013_04
Patent number
US08415333B2

Reaction notes

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