Acetonitrile → HCID 15296958, compound

HRID 2396535Notes

Reaction equation

HRID 2396535 reaction equation
[C:1](#[N:3])[CH3:2].C([N-]C(C)C)(C)C.[Li+].[Cl:12][C:13]1[C:17]([Cl:18])=[C:16]([Cl:19])[S:15][C:14]=1[C:20]#[N:21].Br[CH2:23][C:24]([C:26]([F:29])([F:28])[F:27])=O>O1CCCC1.C(O)(=O)C.O.CCCCCC.C(OCC)(=O)C>[Cl:12][C:13]1[C:17]([Cl:18])=[C:16]([Cl:19])[S:15][C:14]=1[C:20]1[NH:21][C:24]([C:26]([F:29])([F:28])[F:27])=[CH:23][C:2]=1[C:1]#[N:3]

Participants

10

Reactant 4

HCID 6342AcetonitrileHCID 790083-Bromo-1,1,1-trifluoro-2-propanoneHCID 2724682Lithium diisopropylamideHCID 117459463,4,5-Trichloro-2-thiophenecarbonitrile

Product 1

HCID 15296958HCID 15296958, compoundYield 7.8%

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

Acetonitrile (0.97 g, 23.7 mmol) is added dropwise to a solution of lithium diisopropylamide (two molar in hydrocarbons, 10.9 mL, 21.8 mmol) in tetrahydrofuran at -78° C. The reaction mixture is stirred at -78° C. for 30 minutes, treated with a solution of 3,4,5-trichloro-2-thiophenecarbonitrile (3.87 g, 18.2 mmol) in tetrahydrofuran, stirred for 30 minutes at -78° C., warmed to room temperature over 45 minutes, quenched with saturated ammonium chloride solution and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over MgSO4 and concentrated in vacuo to obtain a red solid. A mixture of the red solid and 1-bromo-3,3,3-trifluoroacetone (1.95 mL, 18.7 mmol) in acetic acid is refluxed for three hours and 30 minutes, diluted with water and extracted with ether. The combined organic extracts are washed sequentially with water and brine, dried over MgSO4 and concentrated .in vacuo to obtain a red solid. Flash chromatography of the solid using silica gel and a 15% ethyl acetate in hexane solution gives the title product as a white solid (0.49 g, 7.8%, mp 220°-221° C.).

Workup

  1. stirringstirred for 30 minutes at -78° C.
  2. temperaturewarmed to room temperature over 45 minutes
  3. customquenched with saturated ammonium chloride solution
  4. extractionextracted with ether
  5. washThe combined organic extracts are washed sequentially with water and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customto obtain a red solid
  9. temperatureis refluxed for three hours and 30 minutes
  10. extractionextracted with ether
  11. washThe combined organic extracts are washed sequentially with water and brine
  12. dry with materialdried over MgSO4
  13. concentrationconcentrated .in vacuo
  14. customto obtain a red solid

Sources & evidence

ORD record
ord-aa1f533bc4194927891f40abf8a0d7b4
Source dataset
uspto-grants-1996_02
Patent number
US05492925

Reaction notes

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