Bromoacetonitrile → HCID 18702191, compound

HRID 1075689Notes

Reaction equation

HRID 1075689 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([S:10]([CH2:13][C:14]#[N:15])(=[O:12])=[O:11])=[CH:6][CH:5]=1.Br[CH2:17][C:18]#[N:19]>O1CCCC1>[Cl:3][C:4]1[CH:5]=[CH:6][C:7]([S:10]([CH:13]([CH2:17][C:18]#[N:19])[C:14]#[N:15])(=[O:11])=[O:12])=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 11534BromoacetonitrileHCID 24758Sodium hydrideHCID 7358292-(4-Chlorobenzenesulfonyl)acetonitrile

Product 1

HCID 18702191HCID 18702191, compoundYield 12%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a 500 mL reaction flask was added 2.0 g (51.0 mmole) sodium hydride (60% dispersion in oil) and 20 mL hexanes. The hexanes were removed by pipette and replaced by 90 mL dry tetrahydrofuran (THF). The suspension was cooled to 0° C. and a solution of 10.0 g (46.4 mmole) 4-chlorophenylsulfonyl acetonitrile in 90 mL THF was added via addition funnel over 10 minutes maintaining the reaction temperature below 12° C. The resulting solution was removed from the cold bath and stirred at room temperature for 40 min. The solution was recooled to 0°C. and 3.4 mL (48.7 mmole) bromoacetonitrile in 5 mL THF was added dropwise via addition funnel. After 5 minutes, the reaction was removed from the cold bath and stirred at room temperature for two hours. The reaction was quenched with 1 mL of saturated ammonium chloride and concentrated to an oil which was transferred with 150 mL of dichloromethane to a separatory funnel containing 120 mL water. The organic layer was separated and washed once more with 120 mL water and once with 120 mL brine. The organic layer was then dried (Na2SO4), filtered, concentrated, and chromatographed through a bed of silica gel using 85:15 hexane:ethyl acetate. Isolation gave 1.4 g (12% yield) of the title compound as a yellow powder that was 96% pure by HPLC, m.p. 130-137° C.

Workup

  1. customTo a 500 mL reaction flask
  2. customThe hexanes were removed by pipette
  3. temperaturemaintaining the reaction temperature below 12° C
  4. customThe resulting solution was removed from the cold bath
  5. customwas recooled to 0°C.
  6. waitAfter 5 minutes
  7. customthe reaction was removed from the cold bath
  8. stirringstirred at room temperature for two hours
  9. customThe reaction was quenched with 1 mL of saturated ammonium chloride
  10. concentrationconcentrated to an oil which
  11. customwas transferred with 150 mL of dichloromethane to a separatory funnel
  12. additioncontaining 120 mL water
  13. customThe organic layer was separated
  14. washwashed once more with 120 mL water and once with 120 mL brine
  15. dry with materialThe organic layer was then dried (Na2SO4)
  16. filtrationfiltered
  17. concentrationconcentrated
  18. customchromatographed through a bed of silica gel using 85:15 hexane

Sources & evidence

ORD record
ord-d9c859a9fc1846509a24915e71080fdf
Source dataset
uspto-grants-1999_05
Patent number
US05907041

Reaction notes

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