Water → 1-(3,4-Dichlorophenyl)cyclopent-3-enecarbonitrile

HRID 333273Notes

Reaction equation

HRID 333273 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:5]=[C:6]([CH2:11][C:12]#[N:13])[CH:7]=[CH:8][C:9]=1[Cl:10].Cl/[CH:15]=[CH:16]\[CH2:17][CH2:18]Cl.O>CS(C)=O>[Cl:3][C:4]1[CH:5]=[C:6]([C:11]2([C:12]#[N:13])[CH2:18][CH:17]=[CH:16][CH2:15]2)[CH:7]=[CH:8][C:9]=1[Cl:10]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 76690(3,4-Dichlorophenyl)acetonitrileHCID 86614758HCID 86614758, compound

Product 1

HCID 589548471-(3,4-Dichlorophenyl)cyclopent-3-enecarbonitrileYield 43%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

To ice-cold DMSO (100 mL) was added 60% NaH (1.0 g, 2.3 eq) in portions. The cooling bath was removed and the solution was stirred at ambient temperature for ten minutes. A solution of 2-(3,4-dichlorophenyl)acetonitrile (2.0 g, 10.75 mmol) in DMSO (50 mL) was added. The brown solution was stirred for 15 minutes before cis-1,4-dichlorobutene (1.0 mL, 0.9 eq) was added. The reaction mixture was stirred overnight and was then poured into water. The product was extracted with DCM. The organic layer was washed with brine, evaporated, diluted with 50% ethyl acetate in hexanes, washed with water, and evaporated. The residual oil was separated on silica to give the nitrile (966 mg, 43%) as a pale-brown oil. GCMS Rt=10.8 min m/z=237 (M+). 1H NMR (CDCl3, δ): 7.51 (d, J=2.3 Hz, 1H), 7.39 (d, J=8.5 Hz, 1H), 7.28 (dd, J=2.3, 8.5 Hz, 1H), 5.79 (s, 2H), 3.27 (d, J=14.7 Hz, 2H), 2.87 (d, J=14.7 Hz, 2H). 13C NMR (CDCl3, δ): 141.9, 133.2, 132.1, 131.0, 128.5, 127.6, 125.0, 124.0, 48.4.

Workup

  1. customThe cooling bath was removed
  2. additionwas added
  3. stirringThe reaction mixture was stirred overnight
  4. extractionThe product was extracted with DCM
  5. washThe organic layer was washed with brine
  6. customevaporated
  7. additiondiluted with 50% ethyl acetate in hexanes
  8. washwashed with water
  9. customevaporated
  10. customThe residual oil was separated on silica

Sources & evidence

ORD record
ord-671af1f8b754400da1bdc37835537aa4
Source dataset
uspto-grants-2014_11
Patent number
US08877975B2

Reaction notes

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