Sodium hydride → HCID 53256559, compound

HRID 546078Notes

Reaction equation

HRID 546078 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 79%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Nitro-1H-pyrazole (prepared in example 3, 270 mg, 2.39 mmol) was dissolved in anhydrous N,N-dimethylformamide (3 mL) and a 60% dispersion of sodium hydride in mineral oil (116 mg, 2.90 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 (390 mg, 2.60 mmol) was added. The reaction continued to stir under nitrogen for 2 h. The solution was diluted with ethyl acetate (75 mL), washed with water (2×25 mL), saturated aqueous brine solution (25 mL), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash column chromatography (Merck silica gel 60, 40-63 μm; 20% ethyl acetate/hexanes) afforded 1-(3-methyl-but-2-enyl)-3-nitro-1H-pyrazole (340 mg, 79%) 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 2 h
  3. washwashed with water (2×25 mL), saturated aqueous brine solution (25 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; 20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-a0a4c27fd78f4ef786ebcaa15b5b41f8
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

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