Ammonium → 6-Amino-4-chloro-3-pyridinecarbonitrile

HRID 2376919Notes

Reaction equation

HRID 2376919 reaction equation
[CH3:1][N:2]1CCCC1=O.[NH2:8][C:9]1[CH:14]=[C:13]([Cl:15])[C:12](I)=[CH:11][N:10]=1.[NH4+]>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C>[NH2:8][C:9]1[CH:14]=[C:13]([Cl:15])[C:12]([C:1]#[N:2])=[CH:11][N:10]=1

Participants

7

Reactant 3

HCID 223AmmoniumHCID 13387N-methyl-2-pyrrolidoneHCID 219491214-Chloro-5-iodopyridin-2-amine

Product 1

HCID 219492196-Amino-4-chloro-3-pyridinecarbonitrile

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
132.5 °C

Procedure

1-Methyl-2-pyrrolidone (20 ml), zinc cyanide (0.49 g, 4.17 mmol) and tetrakis(triphenylphosphine)palladium (1.3 g, 1.12 mmol) were added to 2-amino-4-chloro-5-iodopyridine (1.93 g, 7.58 mmol) synthesized in Production example 215-2; and the reaction mixture was stirred at 130-135° C. for 5 hours. Approximately 0.28% of aqueous ammonium (100 ml) and ethyl acetate was added to the reaction mixture; and the organic layer was separated, washed with brine, and dried over anhydrous sodium sulfate. This was concentrated under reduced pressure and the residue was filtrated by silica gel column chromatography (Fuji Silysia NH, ethyl acetate). After concentration under reduced pressure, a solvent mixture (ether:hexane=1:1) was added to the residue, and stirred; and the solid was filtered off to yield the title compound as crystals (680 mg).

Workup

  1. customsynthesized in Production example 215-2
  2. customand the organic layer was separated
  3. washwashed with brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationThis was concentrated under reduced pressure
  6. filtrationthe residue was filtrated by silica gel column chromatography (Fuji Silysia NH, ethyl acetate)
  7. concentrationAfter concentration under reduced pressure
  8. additiona solvent mixture (ether:hexane=1:1) was added to the residue
  9. stirringstirred
  10. filtrationand the solid was filtered off

Sources & evidence

ORD record
ord-46506127f2f642059c0b5da6ad334ad8
Source dataset
uspto-grants-2008_12
Patent number
US07468380B2

Reaction notes

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