1,2-Dibromoethane → HCID 117966431, compound

HRID 931145Notes

Reaction equation

HRID 931145 reaction equation
[H-].[Na+].[CH3:3][S:4][C:5]1[CH:6]=[N:7][N:8]([CH2:10][C:11]#[N:12])[CH:9]=1.Br[CH2:14][CH2:15]Br.[Cl-].[NH4+]>CS(C)=O>[CH3:3][S:4][C:5]1[CH:6]=[N:7][N:8]([C:10]2([C:11]#[N:12])[CH2:15][CH2:14]2)[CH:9]=1

Participants

6

Reactant 4

HCID 78391,2-Dibromoethane2×HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 89854165HCID 89854165, compound

Product 1

HCID 117966431HCID 117966431, compoundYield 22.8%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

To sodium hydride (2.29 g, 57 mmol, 60% dispersion in mineral oil) was added petroleum ether (40 mL). The suspension was stirred for 10 min and the supernatant was removed. Petroleum ether (40 mL) was added again and the suspension was stirred for another 10 min. The supernatant was removed again after the suspension settled in order to remove the mineral oil. Dimethylsulfoxide (25 mL) was slowly added at 20° C. under nitrogen. A solution of 2-(4-(methylthio)-1H-pyrazol-1-yl)acetonitrile (1.46 g, 9.53 mmol) and 1,2-dibromoethane (2.46 mL, 28.5 mmol) in dimethylsulfoxide (23 mL) was added dropwise over a period of 15 minutes. Additional 1,2-dibromoethane (0.5 mL) was added and the reaction mixture was stirred at room temperature for 18 h. The reaction mixture was poured into a cold saturated aqueous solution of ammonium chloride (150 mL). The mixture was stirred for 10 min and then it was extracted with diethyl ether (100 mL×3). The combined organics were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified via flash chromatography (95:5 to 60:40 heptane:ethyl acetate) to afford 1-(4-(methylthio)-1H-pyrazol-1-yl)cyclopropanecarbonitrile (390 mg, 22.8%). 1H NMR (500 MHz, CDCl3) δ 1.79-1.83 (m, 4H), 2.36 (s, 3H), 7.52 (s, 1H), 7.58-7.60 (m, 1H).

Workup

  1. customthe supernatant was removed
  2. additionPetroleum ether (40 mL) was added again
  3. stirringthe suspension was stirred for another 10 min
  4. customThe supernatant was removed again after the suspension
  5. customto remove the mineral oil
  6. additionDimethylsulfoxide (25 mL) was slowly added at 20° C. under nitrogen
  7. stirringthe reaction mixture was stirred at room temperature for 18 h
  8. stirringThe mixture was stirred for 10 min
  9. extractionit was extracted with diethyl ether (100 mL×3)
  10. washThe combined organics were washed with brine
  11. dry with materialdried over sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated under reduced pressure
  14. customThe crude material was purified via flash chromatography (95:5 to 60:40 heptane:ethyl acetate)

Sources & evidence

ORD record
ord-d09a60833f594039b7d7a63a12f6c971
Source dataset
uspto-grants-2016_03
Patent number
US09296745B2

Reaction notes

Loading…