1-((6-methylpyridin-2-yl)methyl)-4-nitro-3-vinyl-1H-indazole → 3-ethyl-((6-methylpyridin-2-yl)methyl)-1H-indazol-4-amine

HRID 79299

Reaction equation

HRID 79299 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]([CH2:8][N:9]2[C:17]3[C:12](=[C:13]([N+:18]([O-])=O)[CH:14]=[CH:15][CH:16]=3)[C:11]([CH:21]=[CH2:22])=[N:10]2)[CH:5]=[CH:4][CH:3]=1>CCO.C(Cl)Cl.[OH-].[Pd+2].[OH-]>[CH2:21]([C:11]1[C:12]2[C:13]([NH2:18])=[CH:14][CH:15]=[CH:16][C:17]=2[N:9]([CH2:8][C:6]2[CH:5]=[CH:4][CH:3]=[C:2]([CH3:1])[N:7]=2)[N:10]=1)[CH3:22]

Participants

4

Reactant 1

HCID 672597031-((6-methylpyridin-2-yl)methyl)-4-nitro-3-vinyl-1H-indazole

Product 1

HCID 672598043-ethyl-((6-methylpyridin-2-yl)methyl)-1H-indazol-4-amineYield 87.8%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 21584144Dichloromethane ethanolSolvent

Procedure

To 1-((6-methylpyridin-2-yl)methyl)-4-nitro-3-vinyl-1H-indazole (28.2 g, 95.8 mmol, Example 5, step C) in EtOH/DCM (300 mL/10 mL) was added palladium hydroxide (15 g, 20% wt). The reaction was purged with N2 and charged with hydrogen to 45 psi. The reaction was recharged during the reaction to 45 psi 4-5 times for the first 30 minutes. After 2 hours, the reaction was stopped, filtered through Celite, and the filter pad was washed with MeOH/DCM/Et3N (1 L, 10:1:1). The filtrate was concentrated and silica gel chromatography (EtOAc/hexanes 1:3) to provide the desired product (22.4 g).

Workup

  1. customThe reaction was purged with N2
  2. additioncharged with hydrogen to 45 psi
  3. customThe reaction was recharged during the reaction to 45 psi 4-5 times for the first 30 minutes
  4. filtrationfiltered through Celite
  5. washthe filter pad was washed with MeOH/DCM/Et3N (1 L, 10:1:1)
  6. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-a4f5e7c48c9143ab82cd155c46a4ec4b
Source dataset
uspto-grants-2014_09
Patent number
US08841455B2

Linked notes

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