N,N'-Dimethylethylenediamine → Benzo[b]thiophene-3-carbonitrile

HRID 2180647Notes

Reaction equation

HRID 2180647 reaction equation
[C-]#N.[Na+].Br[C:5]1[C:6]2[CH:13]=[CH:12][CH:11]=[CH:10][C:7]=2[S:8][CH:9]=1.[CH3:14][NH:15]CCNC.[OH-].[NH4+]>[Cu]I.O.C(OCC)(=O)C.C1(C)C=CC=CC=1>[S:8]1[CH:9]=[C:5]([C:14]#[N:15])[C:6]2[CH:13]=[CH:12][CH:11]=[CH:10][C:7]1=2

Participants

9

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 8929Sodium CyanideHCID 14923Ammonium HydroxideHCID 123250Benzo(b)thiophene, 3-bromo-

Product 1

HCID 11435093Benzo[b]thiophene-3-carbonitrileYield 74.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

An oven dried screw cap test tube was charged with NaCN (60 mg, 1.225 mmol), dried KI (34 mg, 0.205 mmol, 20 mol %) and CuI (20 mg, 0.105 mmol, 10 mol %), evacuated and backfilled with argon three times. 3-Bromo-benzo[b]thiophene (135 μL, 1.032 mmol), N,N′-dimethylethylenediamine (110 μL, 1.033 mmol) and anhydrous toluene (700 μL) were added under argon. The tube was sealed and the reaction mixture was stirred magnetically at 110° C. for 24 h. The resulting suspension was cooled to room temperature, 2 mL of ethyl acetate, 1 mL of ammonium hydroxide (30%) and 1 mL of water were added. The mixture was stirred at 25° C. for 10 min, then the organic layer was separated and the aqueous layer was extracted three times with ethyl acetate (3×2 mL). The combined organic layers were washed with 5 mL of water and dried over MgSO4. The solvent was removed at reduced pressure. Purification of the residue by flash chromatography on silica gel (2×15 cm; hexane/ethyl acetate 10:1) provided 122 mg (74% yield) of the title compound as a pale yellow solid.

Workup

  1. customAn oven dried screw
  2. customcap test tube
  3. customevacuated
  4. customThe tube was sealed
  5. temperatureThe resulting suspension was cooled to room temperature
  6. stirringThe mixture was stirred at 25° C. for 10 min
  7. customthe organic layer was separated
  8. extractionthe aqueous layer was extracted three times with ethyl acetate (3×2 mL)
  9. washThe combined organic layers were washed with 5 mL of water
  10. dry with materialdried over MgSO4
  11. customThe solvent was removed at reduced pressure
  12. customPurification of the residue by flash chromatography on silica gel (2×15 cm; hexane/ethyl acetate 10:1)

Sources & evidence

ORD record
ord-437e072c31fa41e5ab4b7ac8bba8a4d8
Source dataset
uspto-grants-2005_05
Patent number
US06888032B2

Reaction notes

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