Methanol → HCID 67259581, compound

HRID 79258Notes

Reaction equation

HRID 79258 reaction equation
[CH2:1]([N:8]1[C:16]2[C:11](=[C:12]([N+:17]([O-:19])=[O:18])[CH:13]=[CH:14][CH:15]=2)[C:10](I)=[N:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:21]([Zn]CC)[CH3:22].CO.ClCCl>O1CCOCC1>[CH2:1]([N:8]1[C:16]2[C:11](=[C:12]([N+:17]([O-:19])=[O:18])[CH:13]=[CH:14][CH:15]=2)[C:10]([CH2:21][CH3:22])=[N:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 6344DichloromethaneHCID 67259890HCID 67259890, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 67259581HCID 67259581, compoundYield 20.4%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a mixture of 1-benzyl-3-iodo-4-nitro-1H-indazole (304 mg, 0.802 mmol) (prepared as in Example 1, steps E-F) and 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (196 mg, 0.241 mmol) in dioxane (4.0 mL) under an atmosphere of dry nitrogen was added a solution of diethylzinc (1.6 mL, 1.60 mmol; 1 molar in hexane) with magnetic stirring. The mixture was heated at reflux for 2 hours. After allowing to cool methanol (1 mL) was added followed by dichloromethane (30 mL) and the mixture was stirred for 30 minutes. The mixture was transferred to a separatory funnel and washed with water (30 mL). The organic phase was dried over magnesium sulfate, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica, eluting with 15-20% ethyl acetate in hexanes. Fractions containing product were concentrated under reduced pressure to give 1-benzyl-3-ethyl-4-nitro-1H-indazole (46 mg).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 2 hours
  3. additionwas added
  4. customThe mixture was transferred to a separatory funnel
  5. washwashed with water (30 mL)
  6. dry with materialThe organic phase was dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under vacuum
  9. customThe crude product was purified by column chromatography on silica
  10. washeluting with 15-20% ethyl acetate in hexanes
  11. additionFractions containing product
  12. concentrationwere concentrated under reduced pressure

Sources & evidence

ORD record
ord-8d1d9b87f5ed4c04b8aa5baf0dd2cb9a
Source dataset
uspto-grants-2014_09
Patent number
US08841455B2

Reaction notes

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