3-Amino-1H-indazole-6-carbonitrile → 1H-indazole-6-carbonitrile

HRID 842712Notes

Reaction equation

HRID 842712 reaction equation
N([O-])=O.[Na+].N[C:6]1[C:14]2[C:9](=[CH:10][C:11]([C:15]#[N:16])=[CH:12][CH:13]=2)[NH:8][N:7]=1>O.C(O)(=O)C>[C:15]([C:11]1[CH:10]=[C:9]2[C:14]([CH:6]=[N:7][NH:8]2)=[CH:13][CH:12]=1)#[N:16]

Participants

5

Reactant 2

HCID 226152723-Amino-1H-indazole-6-carbonitrileHCID 23668193Sodium Nitrite

Product 1

HCID 4225291H-indazole-6-carbonitrile

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

A solution of sodium nitrite (218 mg, 3.16 mmol) in water (1 mL) was added dropwise over 2 min to a stirred suspension of 3-amino-6-cyanoindazole (250 mg, 1.58 mmol) in water (1 mL) and acetic acid (2 mL) at 0° C. The resulting thick suspension was warmed to rt. After 16 h the mixture was cooled to 0° C. and the solids were collected by filtration, washing with cold water. The solids were suspended in 0.1 M HCl (4 mL), DME (3 mL) was added and the resulting mixture was stirred and heated to 80° C. for 1.5 h. The reaction was cooled and concentrated to ⅓ the volume. The residue was neutralised with sodium bicarbonate and extracted with ethyl acetate. The ethyl acetate layer was washed with water and brine, dried (Na2SO4) and evaporated in vacuo. The residue was purified by chromatography on silica (5:1 chloroform/ethyl acetate) to give the title compound as a yellow solid:

Workup

  1. temperatureAfter 16 h the mixture was cooled to 0° C.
  2. filtrationthe solids were collected by filtration
  3. washwashing with cold water
  4. additionDME (3 mL) was added
  5. temperatureheated to 80° C. for 1.5 h
  6. temperatureThe reaction was cooled
  7. concentrationconcentrated
  8. extractionextracted with ethyl acetate
  9. washThe ethyl acetate layer was washed with water and brine
  10. dry with materialdried (Na2SO4)
  11. customevaporated in vacuo
  12. customThe residue was purified by chromatography on silica (5:1 chloroform/ethyl acetate)

Sources & evidence

ORD record
ord-96678fef222545f19dc2e38318e6d640
Source dataset
uspto-grants-2002_04
Patent number
US06376499B1

Reaction notes

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