Acrylonitrile → 3-[4-(1H-Benzoimidazol-2-yl)-furazan-3-ylamino]-propionitrile

HRID 2405029Notes

Reaction equation

HRID 2405029 reaction equation
[NH:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:2]1[C:10]1[C:11]([NH2:15])=[N:12][O:13][N:14]=1.C[O-].[Na+].[C:19](#[N:22])[CH:20]=[CH2:21]>N1C=CC=CC=1>[NH:3]1[C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=2[N:1]=[C:2]1[C:10]1[C:11]([NH:15][CH2:21][CH2:20][C:19]#[N:22])=[N:12][O:13][N:14]=1

Participants

5

Reactant 3

HCID 7855AcrylonitrileHCID 7385314-(1H-benzimidazol-2-yl)-1,2,5-oxadiazol-3-amineHCID 10942334Sodium Methoxide

Product 1

HCID 1363893133-[4-(1H-Benzoimidazol-2-yl)-furazan-3-ylamino]-propionitrileYield 48.2%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To an ice-cooled, stirred solution of 18.2 g of 4-(1H-benzoimidazol-2-yl)-furazan-3-ylamine (90.5 mmol, 1 eq) in 240 ml of pyridine are added 30 ml of sodium methoxide solution (30% in MeOH) (163 mmol, 1.8 eq) and subsequently 6 ml of acrylonitrile (90.5 mmol, 1 eq). The reaction mixture is stirred at room temperature overnight, before it is concentrated under reduced pressure. The residue is suspended in 250 ml of water and extracted with 4×400 ml of ethyl acetate. The combined organic layers are washed with 2×500 ml of brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The crude product is dissolved in about 1000 ml of refluxing ethyl acetate. Then 1700 ml of n-hexane are added to the solution. The resulting turbid mixture is allowed to stand at room temperature overnight and the formed precipitate is filtered to provide 11.1 g of the product as light yellow solid. The filtrate is concentrated to dryness under reduced pressure and the residue is suspended in 100 ml of a 1/1 mixture of n-hexane/ethyl acetate. The suspension is filtered to provide 4.7 g additional product.

Workup

  1. concentrationis concentrated under reduced pressure
  2. extractionextracted with 4×400 ml of ethyl acetate
  3. washThe combined organic layers are washed with 2×500 ml of brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe crude product is dissolved in about 1000 ml of refluxing ethyl acetate
  8. additionThen 1700 ml of n-hexane are added to the solution
  9. waitto stand at room temperature overnight
  10. filtrationthe formed precipitate is filtered

Sources & evidence

ORD record
ord-66cace36e9e8408da186a7b76f9ab995
Source dataset
uspto-grants-2014_08
Patent number
US08802858B2

Reaction notes

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