Hydroxyamine hydrochloride → 7-Bromo-4-(N-hydroxy-imino)-1-(2-pyridyl)-3,6,6-trimethyl-4,5,6,7-tetrahydroindazole

HRID 2084286

Reaction equation

HRID 2084286 reaction equation
[Br:1][CH:2]1[C:10]2[N:9]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][N:12]=3)[N:8]=[C:7]([CH3:17])[C:6]=2[C:5](=O)[CH2:4][C:3]1([CH3:20])[CH3:19].Cl.[NH2:22][OH:23].C([O-])(=O)C.[Na+]>O1CCOCC1>[Br:1][CH:2]1[C:10]2[N:9]([C:11]3[CH:16]=[CH:15][CH:14]=[CH:13][N:12]=3)[N:8]=[C:7]([CH3:17])[C:6]=2[C:5](=[N:22][OH:23])[CH2:4][C:3]1([CH3:20])[CH3:19]

Participants

5

Reactant 3

HCID 443297Hydroxyamine hydrochloride2×HCID 517045Sodium Acetate2×HCID 40739867-Bromo-3,6,6-trimethyl-1-pyridin-2-yl-5,7-dihydroindazol-4-one

Product 1

HCID 571058077-Bromo-4-(N-hydroxy-imino)-1-(2-pyridyl)-3,6,6-trimethyl-4,5,6,7-tetrahydroindazoleYield 45%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A mixture of 7-bromo-1-(2-pyridyl)-3,6,6-trimethyl-4-oxo-4,5,6,7-tetrahydro-indazole (0.3 g, 0.9 mmol), prepared as described in example 4, hydroxylamine hydrochloride (0.37 g, 4.5 mmol), and sodium acetate (0.44 g, 5.4 mmol) in 1,4-dioxane (50 ml) was heated under reflux for about 4 hours. Additional hydroxylamine hydrochloride (0.123 g, 1.6 eq) and sodium acetate (0.146 g, 2 eq) were added and heating was continued for further 4 hours. The reaction mixture was poured onto ice/water and extracted with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate and evaporated. The residue was chromatographed on silica gel (cyclohexane:ethyl acetate=90:10) to give the title compound as a colourless solid (0.14 g, 45%): m.p. 195-196° C.

Workup

  1. customprepared
  2. temperaturewas heated
  3. temperatureunder reflux for about 4 hours
  4. temperatureheating
  5. additionThe reaction mixture was poured onto ice/water
  6. extractionextracted with dichloromethane
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over sodium sulfate
  9. customevaporated
  10. customThe residue was chromatographed on silica gel (cyclohexane:ethyl acetate=90:10)

Sources & evidence

ORD record
ord-8fa14da4604641c0ae2faca3d132a82c
Source dataset
uspto-grants-2004_04
Patent number
US06716856B1

Linked notes

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