Sodium hydride → HCID 53256559, compound

HRID 546075Notes

Reaction equation

HRID 546075 reaction equation
[N+:1]([C:4]1[CH:8]=[CH:7][NH:6][N:5]=1)([O-:3])=[O:2].[H-].[Na+].Br[CH2:12][CH:13]=[C:14]([CH3:16])[CH3:15]>CN(C)C=O.C(OCC)(=O)C>[CH3:15][C:14]([CH3:16])=[CH:13][CH2:12][N:6]1[CH:7]=[CH:8][C:4]([N+:1]([O-:3])=[O:2])=[N:5]1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 700922-Butene, 1-bromo-3-methyl-HCID 178526745HCID 178526745, compound

Product 1

HCID 53256559HCID 53256559, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Nitro-1H-pyrazole (prepared in example 3, 1.00 g, 8.85 mmol) was dissolved in anhydrous N,N-dimethylformamide (10 mL) and a 60% dispersion of sodium hydride in mineral oil (390 mg, 9.74 mmol) was added while stirring under nitrogen. After the effervescence ceased and the reaction stirred for an additional 10 min, the 1-bromo-3-methyl-but-2-ene (1.33 g, 9.00 mmol) was added. The reaction continued to stir under nitrogen for 20 min. The solution was diluted with ethyl acetate (200 mL), washed with water (2×75 mL), saturated aqueous brine solution (75 mL), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash column chromatography (Merck silica gel 60, 40-63 μm; 5% ethyl acetate/hexanes to 20% ethyl acetate/hexanes) afforded 1-(3-methyl-but-2-enyl)-3-nitro-1H-pyrazole (1.29 g, 81%) as a yellow oil: H1-NMR (400 MHz, CDCl3) δ 1.79 (3H, s), 1.83 (3H, s), 4.80 (2H, d, J=7.2 Hz), 5.45 (1H, t, J=7.2 Hz), 6.88 (1H, s), 7.43 (1H, s).

Workup

  1. stirringthe reaction stirred for an additional 10 min
  2. stirringto stir under nitrogen for 20 min
  3. washwashed with water (2×75 mL), saturated aqueous brine solution (75 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash column chromatography (Merck silica gel 60, 40-63 μm; 5% ethyl acetate/hexanes to 20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-28cc493b0ddd4c109ee7b2ea7e686673
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

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