Dichloromethane → 3-(4-Fluorophenyl)-5-nitro-1H-indazole

HRID 227699Notes

Reaction equation

HRID 227699 reaction equation
Br[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([N+:11]([O-:13])=[O:12])[CH:9]=2)[N:4](C(OC(C)(C)C)=O)[N:3]=1.[F:21][C:22]1[CH:27]=[CH:26][C:25](B(O)O)=[CH:24][CH:23]=1.C(Cl)Cl.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[F:21][C:22]1[CH:27]=[CH:26][C:25]([C:2]2[C:10]3[C:5](=[CH:6][CH:7]=[C:8]([N+:11]([O-:13])=[O:12])[CH:9]=3)[NH:4][N:3]=2)=[CH:24][CH:23]=1

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 2856454-Fluorophenylboronic acidHCID 222608361-Boc-3-bromo-5-nitro-1H-indazole

Product 1

HCID 534397423-(4-Fluorophenyl)-5-nitro-1H-indazoleYield 100%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
95 °C

Procedure

The product from Step (b) (0.5 g, 1.5 mmol), 4-fluoro phenylboronic acid (0.31 g, 2.2 mmol) and Pd(dppf)2Cl2.CH2Cl2 (0.12 g, 0.15 mmol) were combined in 9 ml of 2:1 Dioxane/2 M K2CO3 The reaction mixture was sealed and heated to 95° C. for 18 h. The resulting biphasic mixture was cooled to room temperature. The phases were separated and the organic phase (top) was filtered. The aqueous layer was extracted once with EtOAc. The combined organic phases were washed with sat'd NaHCO3, water, brine, dried (Na2SO4) and concentrated in vacuo. The residue was purified by silica gel chromatography (5% MeOH/CH2Cl2) to afford 0.37 g of the title compound, (100%); MS (ES+) m/e 259 [M+H]+.

Workup

  1. customwas sealed
  2. temperatureThe resulting biphasic mixture was cooled to room temperature
  3. customThe phases were separated
  4. filtrationthe organic phase (top) was filtered
  5. extractionThe aqueous layer was extracted once with EtOAc
  6. washThe combined organic phases were washed with sat'd NaHCO3, water, brine
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by silica gel chromatography (5% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-26ae3449e1e54625a1aa31e2d7e2bb03
Source dataset
uspto-grants-2009_07
Patent number
US07560467B2

Reaction notes

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