Cesium carbonate → 3-ethyl-1-phenyl-1H-indazol-6-amine

HRID 68693Notes

Reaction equation

HRID 68693 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([C:6]([CH2:17][CH3:18])=[N:7][N:8]2[C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[CH:4][CH:3]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[Cs+].[Cs+].C1(C(C2C=CC=CC=2)=[NH:74])C=CC=CC=1>O1CCCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:17]([C:6]1[C:5]2[C:9](=[CH:10][C:2]([NH2:74])=[CH:3][CH:4]=2)[N:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:7]=1)[CH3:18]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 136809Benzophenone imineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 674494686-bromo-3-ethyl-1-phenyl-1H-indazole

Product 1

HCID 674492303-ethyl-1-phenyl-1H-indazol-6-amine

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Into a 100-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of 6-bromo-3-ethyl-1-phenyl-1H-indazole (300 mg, 1.00 mmol, 1.00 equiv) in tetrahydrofuran (30 mL), Xantphos (64 mg, 0.11 mmol, 0.11 equiv), Pd(OAc)2 (33 mg, 0.15 mmol, 0.15 equiv), Cs2CO3 (214 mg, 1.11 mmol, 1.11 equiv), diphenylmethanimine (200 mg, 1.10 mmol, 1.10 equiv). The resulting solution was heated to reflux for 16 h in an oil bath. The resulting mixture was concentrated under vacuum. The residue was dissolved in tetrahydrofuran/3N hydrogen chloride (15 mL/5 mL). The resulting solution was stirred for an additional 2 h at room temperature, then concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate:MeOH:NH4OH (30:1:0.3) to yield 3-ethyl-1-phenyl-1H-indazol-6-amine as yellow oil.

Workup

  1. customInto a 100-mL 3-necked round-bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. temperatureThe resulting solution was heated
  4. temperatureto reflux for 16 h in an oil bath
  5. concentrationThe resulting mixture was concentrated under vacuum
  6. dissolutionThe residue was dissolved in tetrahydrofuran/3N hydrogen chloride (15 mL/5 mL)
  7. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-0be362da01f74ee180311003e9d2e7ed
Source dataset
uspto-grants-2014_09
Patent number
US08822447B2

Reaction notes

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