Allyl bromide → HCID 57642378, compound

HRID 2112542Notes

Reaction equation

HRID 2112542 reaction equation
[Cl:1][C:2]1[NH:6][N:5]=[C:4]([CH3:7])[C:3]=1[N+:8]([O-:10])=[O:9].[H-].[Li+].[CH2:13](Br)[CH:14]=[CH2:15]>O1CCCC1>[Cl:1][C:2]1[C:3]([N+:8]([O-:10])=[O:9])=[C:4]([CH3:7])[N:5]([CH2:15][CH:14]=[CH2:13])[N:6]=1.[Cl:1][C:2]1[N:6]([CH2:15][CH:14]=[CH2:13])[N:5]=[C:4]([CH3:7])[C:3]=1[N+:8]([O-:10])=[O:9]

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 62714Lithium hydrideHCID 178434618HCID 178434618, compound

Product 2

HCID 57642378HCID 57642378, compoundHCID 68803394HCID 68803394, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 5.0 g (0.031 mole) of 5-chloro-3-methyl-4-nitro-1H-pyrazole in 100 mL of anhydrous tetrahydrofuran under argon, was added 0.37 g (0.0464 mole) of lithium hydride. The mixture was stirred at room temperature for 15 minutes. Then 5.6 g (0.0464 mole) of allyl bromide was added, and the mixture was heated at 80° C. for 10 hours. The mixture was cooled, poured onto ice and extracted twice with ethyl acetate. The combined ethyl acetate layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography, eluting with ethyl acetate-hexane (1:2) to give, as the more polar component, 1.36 g of 3-chloro-5-methyl-4-nitro-1-(2-propenyl)-1H-pyrazole as a colorless oil and, as the less polar component, 0.5 g of 5-chloro-3-methyl-4-nitro-1-(2-propenyl)-1H-pyrazole (XX) as a colorless oil.

Workup

  1. temperaturethe mixture was heated at 80° C. for 10 hours
  2. temperatureThe mixture was cooled
  3. additionpoured onto ice
  4. extractionextracted twice with ethyl acetate
  5. dry with materialThe combined ethyl acetate layers were dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel chromatography
  9. washeluting with ethyl acetate-hexane (1:2)

Sources & evidence

ORD record
ord-20509b9937164ae89d403332317004b8
Source dataset
uspto-grants-2009_04
Patent number
US07524840B2

Reaction notes

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