Heptane → HCID 18373193, compound

HRID 1038841Notes

Reaction equation

HRID 1038841 reaction equation
[CH3:1][C:2]1[C:10]2[C:5](=[CH:6][C:7]([N+:11]([O-])=O)=[CH:8][CH:9]=2)[N:4]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[N:3]=1.CCCCCCC>CCO.C(Cl)Cl.[Pd]>[NH2:11][C:7]1[CH:6]=[C:5]2[C:10]([C:2]([CH3:1])=[N:3][N:4]2[C:14]([O:16][C:17]([CH3:19])([CH3:18])[CH3:20])=[O:15])=[CH:9][CH:8]=1

Participants

6

Reactant 2

HCID 8900HeptaneHCID 18373190HCID 18373190, compound

Product 1

HCID 18373193HCID 18373193, compoundYield 69.2%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

tert-Butyl 3-methyl-6-nitro-1H-indazole-1-carboxylate (7.40 g, 26.7 mmol) was dissolved in EtOH (534 mL). To the solution was added Pd/C (10 wt %, 1.42 g, 1.33 mmol). The mixture was flushed with H2, and placed under an atmosphere of H2 at atmospheric pressure at rt for about 6 h. The mixture was filtered through Celite® and washed through with MeOH. The solvents were removed under reduced pressure. The residue was purified by column chromatography (120 g silica gel) eluting with 20-80% EtOAc/heptane to give a solid. The solid redissolved in DCM (20 mL) and heptane (50 mL) was added. The mixture was concentrated to remove the DCM. The resulting precipitate was collected by vacuum filtration and washed with heptane (20 mL) to provide tert-butyl 6-amino-3-methyl-1H-indazole-1-carboxylate (4.57 g, 69%): LCMS (Table 2, Method c) Rt=1.81 min.; MS m/z: 248 (M+H)+, 1H NMR (400 MHz, DMSO-d6) δ 7.36 (d, J=8.5 Hz, 1H), 7.14 (d, J=1.7 Hz, 1H), 6.59 (dd, J=8.5, 1.9 Hz, 1H), 5.71 (d, J=19.5 Hz, 2H), 2.33 (s, 3H), 1.58 (s, 9H).

Workup

  1. customThe mixture was flushed with H2
  2. filtrationThe mixture was filtered through Celite®
  3. washwashed through with MeOH
  4. customThe solvents were removed under reduced pressure
  5. customThe residue was purified by column chromatography (120 g silica gel)
  6. washeluting with 20-80% EtOAc/heptane
  7. customto give a solid
  8. concentrationThe mixture was concentrated
  9. customto remove the DCM
  10. filtrationThe resulting precipitate was collected by vacuum filtration
  11. washwashed with heptane (20 mL)

Sources & evidence

ORD record
ord-603809b3ef964718ac9e4ae539ab65c5
Source dataset
uspto-grants-2013_10
Patent number
US08551981B2

Reaction notes

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