Ammonium Chloride → 3-((4-amino-1H-indazol-1-yl)methyl)-N,N-dimethylbenzamide

HRID 706679Notes

Reaction equation

HRID 706679 reaction equation
I[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][C:9]=2[N+:11]([O-])=O)[N:4]([CH2:14][C:15]2[CH:16]=[C:17]([CH:23]=[CH:24][CH:25]=2)[C:18]([N:20]([CH3:22])[CH3:21])=[O:19])[N:3]=1.[NH4+].[Cl-]>CO.[Zn]>[NH2:11][C:9]1[CH:8]=[CH:7][CH:6]=[C:5]2[C:10]=1[CH:2]=[N:3][N:4]2[CH2:14][C:15]1[CH:16]=[C:17]([CH:23]=[CH:24][CH:25]=1)[C:18]([N:20]([CH3:22])[CH3:21])=[O:19]

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 679762773-((3-iodo-4-nitro-1H-indazol-1-yl)methyl)-N,N-dimethylbenzamide

Product 1

HCID 679763453-((4-amino-1H-indazol-1-yl)methyl)-N,N-dimethylbenzamideYield 61.2%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 887MethanolSolvent2×

Procedure

A solution of 3-((3-iodo-4-nitro-1H-indazol-1-yl)methyl)-N,N-dimethylbenzamide (0.400 g, 0.888 mmol) and MeOH (8.8 mL) was cooled to 0° C. Zinc dust (0.290 g, 4.44 mmol) was added and the mixture was stirred vigorously for 15 minutes, followed by the dropwise addition of saturated aqueous NH4Cl (9 mL). The mixture was stirred vigorously for 15 minutes at 0° C. and then warmed to ambient temperature and stirred for an additional 1 hour. The mixture was diluted with MeOH and filtered. To the filtrate was added saturated aqueous NH4OAc and the mixture was concentrated to remove bulk MeOH. The mixture was extracted with EtOAc and the combined organic extracts were washed with saturated aqueous NaHCO3 and brine, dried over Na2SO4, filtered and concentrated. The crude product was purified by column chromatography (2 to 20% IPA/CHCl3) to afford 0.160 g (61%) of the title compound as a yellow/orange solid.

Workup

  1. stirringThe mixture was stirred vigorously for 15 minutes at 0° C.
  2. stirringstirred for an additional 1 hour
  3. filtrationfiltered
  4. additionTo the filtrate was added saturated aqueous NH4OAc
  5. concentrationthe mixture was concentrated
  6. customto remove bulk MeOH
  7. extractionThe mixture was extracted with EtOAc
  8. washthe combined organic extracts were washed with saturated aqueous NaHCO3 and brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude product was purified by column chromatography (2 to 20% IPA/CHCl3)

Sources & evidence

ORD record
ord-9533a1c4596d44629597e203baa460ac
Source dataset
uspto-grants-2015_11
Patent number
US09174981B2

Reaction notes

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