Ammonium Chloride → 1-Methyl-5-((methyl(oxetan-3-yl)amino)methyl)-1H-pyrazol-3-amine

HRID 593101Notes

Reaction equation

HRID 593101 reaction equation
[CH3:1][N:2]([CH2:7][C:8]1[N:12]([CH3:13])[N:11]=[C:10]([N+:14]([O-])=O)[CH:9]=1)[CH:3]1[CH2:6][O:5][CH2:4]1.[NH4+].[Cl-]>C(O)C.O.[Fe]>[CH3:13][N:12]1[C:8]([CH2:7][N:2]([CH3:1])[CH:3]2[CH2:4][O:5][CH2:6]2)=[CH:9][C:10]([NH2:14])=[N:11]1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 58043818N-Methyl-N-((1-methyl-3-nitro-1H-pyrazol-5-yl)methyl)oxetan-3-amine

Product 1

HCID 580437871-Methyl-5-((methyl(oxetan-3-yl)amino)methyl)-1H-pyrazol-3-amineYield 83.2%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 302b (1.8 g, 7.96 mmol) in ethanol (20 mL) and water (20 mL), NH4Cl (3.3 g, 63.6 mmol) and iron powder (1.80 g, 31.8 mmol) were added. The reaction mixture was heated at 70° C. for 2 h. After that, the mixture was cooled to room temperature and filtered. The filtrate was evaporated and the residue was extracted with methylene chloride (3×30 mL), dried Na2SO4, and concentrated to afford the crude product, which was purified on flash column eluting with 50:1 methylene chloride/methanol containing 0.5% triethylamine to afford 302c as a yellow oil (1.3 g, 83%). LCMS: (M+H)+ 197

Workup

  1. temperatureAfter that, the mixture was cooled to room temperature
  2. filtrationfiltered
  3. customThe filtrate was evaporated
  4. extractionthe residue was extracted with methylene chloride (3×30 mL), dried Na2SO4
  5. concentrationconcentrated
  6. customto afford the crude product, which
  7. customwas purified on flash column
  8. washeluting with 50:1 methylene chloride/methanol containing 0.5% triethylamine

Sources & evidence

ORD record
ord-9c2b11e4e7444e639b66a51d4bb0fcfb
Source dataset
uspto-grants-2016_01
Patent number
US09238655B2

Reaction notes

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