Acetic Anhydride → HCID 22472992, compound

HRID 2183728Notes

Reaction equation

HRID 2183728 reaction equation
[CH3:1][C:2]1[CH:7]=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][N:10]=2)[CH:5]=[CH:4][C:3]=1[NH2:18].C([O-])(=O)C.[K+].C(OC(=O)C)(=O)C.[N:31](OCCC(C)C)=O>C1(C)C=CC=CC=1>[N+:15]([C:12]1[CH:13]=[CH:14][C:9]([O:8][C:6]2[CH:7]=[C:2]3[C:3](=[CH:4][CH:5]=2)[NH:18][N:31]=[CH:1]3)=[N:10][CH:11]=1)([O-:17])=[O:16]

Participants

6

Reactant 4

HCID 7918Acetic AnhydrideHCID 8053Isoamyl NitriteHCID 517044Potassium AcetateHCID 22472953HCID 22472953, compound

Product 1

HCID 22472992HCID 22472992, compoundYield 20.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 2-methyl-4-(5-nitro-pyridin-2-yloxy)-phenylamine (10 g, 41 mmol), potassium acetate (17 g, 160 mmol), acetic anhydride (17 g, 160 mmol) and toluene (140 mL) at 80° C. was added isoamyl nitrite (9.6 g, 82 mmol) dropwise via an addition funnel. After stirring for 24 h at 80° C., the mixture was filtered, and the filtrate was concentrated in vacuo. The residue was treated with methanol (120 mL) containing 12 mL of concentrated ammonium hydroxide. After refluxing for 2 h, the mixture was cooled to room temperature and was concentrated in vacuo. The residue was purified by silica gel chromatography eluting with ethyl acetate-hexane to afford 2.2 g of 5-(5-Nitro-pyridin-2-yloxy)-1H-indazole as an orange solid. 1H NMR (CD3OD, 400 MHz): δ 8.96 (d, 1H, J=2.4 Hz), 8.56 (dd, 1H, J=2.8, 9.2 Hz), 8.05 (s, 1H), 7.60 (1H, d, 8.8 Hz), 7.56 (m, 1H), 7.21 (dd, 1H, J=2.0, 8.8 Hz), 7.13 (d, 1H, 9.2 Hz) ppm.

Workup

  1. filtrationthe mixture was filtered
  2. concentrationthe filtrate was concentrated in vacuo
  3. additionThe residue was treated with methanol (120 mL)
  4. additioncontaining 12 mL of concentrated ammonium hydroxide
  5. temperatureAfter refluxing for 2 h
  6. temperaturethe mixture was cooled to room temperature
  7. concentrationwas concentrated in vacuo
  8. customThe residue was purified by silica gel chromatography
  9. washeluting with ethyl acetate-hexane

Sources & evidence

ORD record
ord-a07d4dfd27214de4a25054b9734cb0dd
Source dataset
uspto-grants-2005_05
Patent number
US06900201B2

Reaction notes

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