Allyl bromide → HCID 57418747, compound

HRID 1897435Notes

Reaction equation

HRID 1897435 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][N:6]=[CH:5]2.[CH2:11](Br)[CH:12]=[CH2:13].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[CH2:13]([N:7]1[C:8]2[C:4](=[CH:3][C:2]([Br:1])=[CH:10][CH:9]=2)[CH:5]=[N:6]1)[CH:12]=[CH2:11]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 7619295-bromo-1H-indazole

Product 1

HCID 57418747HCID 57418747, compoundYield 36%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

5-Bromoindazole (Bioorg. Med. Chem. Lett., 11:1153-1156 (2001)) (3.94 g, 20.0 mmol), allyl bromide (2.6 mL, 30 mmol) and potassium carbonate (4.15 g, 30.0 mmol) were heated in DMF (25 mL) at 100° C. for 18 hours. The reaction was cooled, filtered through celite, and the solids were washed with EtOAc. The solution was concentrated to near dryness and then partitioned between EtOAc and water. The organic phase was washed with NaHCO3, dried (MgSO4), concentrated, and purified by column chromatography (silica gel, 7% EtOAc/hexanes) to provide the N1 isomer (faster eluting) 1-allyl-5-bromo-1H-indazole (1s) (1.7 g, 36% yield). 1H NMR (400 MHz, CDCl3) δ 7.95 (s, 1H), 7.88 (d, J=2.3 Hz, 1H), 7.44 (dd, J=8.6, 1.6 Hz, 1H), 7.29 (d, J=8.6 Hz, 1H), 6.06-5.97 (m, 1H), 5.24 (dd, J=10.2, 1.6 Hz, 1H), 5.12 (d, J=16.4 Hz, 1H), 5.01-5.00 (m, 2H); MS (ESI+) m/z 237, 239 (M+H, Br pattern) detected; HPLC (5 to 95%) 2.98 min.

Workup

  1. temperatureThe reaction was cooled
  2. filtrationfiltered through celite
  3. washthe solids were washed with EtOAc
  4. concentrationThe solution was concentrated
  5. custompartitioned between EtOAc and water
  6. washThe organic phase was washed with NaHCO3
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. custompurified by column chromatography (silica gel, 7% EtOAc/hexanes)
  10. customto provide the N1 isomer (

Sources & evidence

ORD record
ord-5d42f746119a4b27ad96c90e452ea793
Source dataset
uspto-grants-2013_08
Patent number
US08518983B2

Reaction notes

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