Cesium carbonate → 4-Nitro-1-(oxetan-3-ylmethyl)pyrazole

HRID 1915874Notes

Reaction equation

HRID 1915874 reaction equation
[N+:1]([C:4]1[CH:5]=[N:6][NH:7][CH:8]=1)([O-:3])=[O:2].CS(O[CH2:14][CH:15]1[CH2:18][O:17][CH2:16]1)(=O)=O.C(=O)([O-])[O-].[Cs+].[Cs+].[Cl-].[NH4+]>C(#N)C>[N+:1]([C:4]1[CH:5]=[N:6][N:7]([CH2:14][CH:15]2[CH2:18][O:17][CH2:16]2)[CH:8]=1)([O-:3])=[O:2]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 163764-nitro-1H-pyrazoleHCID 25517Ammonium ChlorideHCID 86680078Oxetan-3-ylmethyl methanesulfonate

Product 1

HCID 866800794-Nitro-1-(oxetan-3-ylmethyl)pyrazoleYield 99.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 4-nitropyrazole (1000 mg, 8.80 mmol), oxetan-3-ylmethyl methanesulfonate (1.90 g, 11.0 mmol), cesium carbonate (8.70 g, 27.0 mmol) and acetonitrile (13 mL) was heated at 100° C. for 3 h. The mixture was cooled to room temperature, saturated ammonium chloride was added. The mixture was extracted with methylene chloride 3×. Combined organics were dried (Na2SO4) and the solvent removed under reduced pressure. The crude product was purified by flash chromatography eluting with 0 to 70% ethyl acetate in heptane to give 4-nitro-1-(oxetan-3-ylmethyl)pyrazole (1.60 g, 99%).

Workup

  1. temperatureThe mixture was cooled to room temperature
  2. extractionThe mixture was extracted with methylene chloride 3×
  3. dry with materialCombined organics were dried (Na2SO4)
  4. customthe solvent removed under reduced pressure
  5. customThe crude product was purified by flash chromatography
  6. washeluting with 0 to 70% ethyl acetate in heptane

Sources & evidence

ORD record
ord-9546f465bc7847849047bc623744a25c
Source dataset
uspto-grants-2013_12
Patent number
US08614206B2

Reaction notes

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