Ethanol → 5-(3-Oxetanyl)-1H-pyrazol-3-amine

HRID 475083Notes

Reaction equation

HRID 475083 reaction equation
CC1[N:3]([C:8]2[CH:12]=[C:11]([CH:13]3[CH2:16][O:15][CH2:14]3)[NH:10][N:9]=2)C(C)=CC=1.CCO.NO.Cl.C([O-])(O)=O.[Na+]>O>[O:15]1[CH2:16][CH:13]([C:11]2[NH:10][N:9]=[C:8]([NH2:3])[CH:12]=2)[CH2:14]1

Participants

6

Reactant 4

HCID 702EthanolHCID 443297Hydroxyamine hydrochlorideHCID 516892Sodium BicarbonateHCID 71272738HCID 71272738, compound

Product 1

HCID 866946865-(3-Oxetanyl)-1H-pyrazol-3-amineYield 19.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

Into a 250-mL 3-necked round-bottom was placed 3-(2,5-dimethyl-1H-pyrrol-1-yl)-5-(oxetan-3-yl)-1H-pyrazole (4.0 g, 18.4 mmol, 1.0 equiv.), EtOH (100 mL), water (40 mL), and NH2OH.HCl (10.3 g, 148.2 mmol, 8.0 equiv.), followed by the addition of NaHCO3 (9.9 g, 117.8 mmol, 6.4 equiv.) portionwise. The resulting solution was stirred at 100° C. for 24 h, then cooled to 30° C. and concentrated in vacuo. The residue was diluted with 150 mL of THF. The solids were collected by filtration and dissolved in 200 mL of EtOH, filtered and the filtrate concentrated in vacuo. The residue was purified by chromatography on neutral alumina eluting with a DCM/MeOH gradient (1 to 10% MeOH) to afford 0.5 g (19%) of 5-(oxetan-3-yl)-1H-pyrazol-3-amine (91) as a white solid.

Workup

  1. temperaturecooled to 30° C.
  2. concentrationconcentrated in vacuo
  3. additionThe residue was diluted with 150 mL of THF
  4. filtrationThe solids were collected by filtration
  5. dissolutiondissolved in 200 mL of EtOH
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated in vacuo
  8. customThe residue was purified by chromatography on neutral alumina eluting with a DCM/MeOH gradient (1 to 10% MeOH)

Sources & evidence

ORD record
ord-c9772f475baa48fbad338b4fdcdc3cf4
Source dataset
uspto-grants-2014_01
Patent number
US08637537B2

Reaction notes

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