4-Bromopyrazole → 4-bromo-1-[(3-methyloxetan-3-yl)methyl]-1H-pyrazole

HRID 1367587Notes

Reaction equation

HRID 1367587 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:5]=[N:6][NH:7][CH:8]=1.Br[CH2:10][C:11]1([CH3:15])[CH2:14][O:13][CH2:12]1>CN(C=O)C.C([O-])(O)=O.[Na+]>[Br:3][C:4]1[CH:5]=[N:6][N:7]([CH2:10][C:11]2([CH3:15])[CH2:14][O:13][CH2:12]2)[CH:8]=1

Participants

6

Reactant 3

HCID 163754-BromopyrazoleHCID 24758Sodium hydrideHCID 144860Oxetane, 3-(bromomethyl)-3-methyl-

Product 1

HCID 669188914-bromo-1-[(3-methyloxetan-3-yl)methyl]-1H-pyrazoleYield 94.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent3×HCID 516892Sodium BicarbonateSolvent

Procedure

To a suspension of NaH (98 mg, 55% in mineral oil, 2.25 mmol) in DMF (1.2 ml) was added a solution of 4-bromopyrazole (300 mg, 2.04 mmol) in DMF (2 ml). The reaction mixture was stirred at room temperature for 15 minutes before a solution of 3-bromomethyl-3-methyloxetane (404 mg, 2.45 mmol) in DMF (2 ml) was added slowly. The mixture was stirred at room temperature for 1.5 h, then diluted with saturated NaHCO3 solution and extracted with 3 times with EtOAc. The combined organic layers were washed 2 times with water and with brine, dried (Na2SO4) and evaporated. The remaining colorless oil was purified by silica gel chromatography (heptane/EtOAc 80:20-50:50) to obtain the title compound (444 mg, 94%) as colorless oil. MS (EI): 231.2 (M+H)+.

Workup

  1. additionwas added slowly
  2. extractionextracted with 3 times with EtOAc
  3. washThe combined organic layers were washed 2 times with water
  4. dry with materialwith brine, dried (Na2SO4)
  5. customevaporated
  6. customThe remaining colorless oil was purified by silica gel chromatography (heptane/EtOAc 80:20-50:50)

Sources & evidence

ORD record
ord-90153202bc004087b74a34b80e0af29e
Source dataset
uspto-grants-2011_02
Patent number
US07893099B2

Reaction notes

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