Cesium fluoride → 4-(p-Chlorophenyl)-3-fluoro-4-methyl-2-pentenenitrile

HRID 610848Notes

Reaction equation

HRID 610848 reaction equation
[F-:1].[Cs+].F.[K].[Cl:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]([CH3:18])([CH3:17])[C:13]#[C:14][C:15]#[N:16])=[CH:8][CH:7]=1.C(OCC)(=O)C.CCCCCC>CN(C)C=O.O>[Cl:5][C:6]1[CH:7]=[CH:8][C:9]([C:12]([CH3:18])([CH3:17])[C:13]([F:1])=[CH:14][C:15]#[N:16])=[CH:10][CH:11]=1

Participants

7

Reactant 4

HCID 25953Cesium fluorideHCID 21226206Ethyl acetate hexaneHCID 219955344-(p-Chlorophenyl)-4-methyl-2-pentynenitrileHCID 53443437Potassium fluoride, 99%, spray-dried

Product 1

HCID 542690284-(p-Chlorophenyl)-3-fluoro-4-methyl-2-pentenenitrileYield 76.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent2×

Procedure

A mixture of cesium fluoride (41.38 g, 0.272 mol), potassium hydrogen fluoride (10.64 g, 0.136 mol) and water (13.07 g, 0.726 mol) in N,N-dimethylformamide is stirred for 10 minutes, treated with a solution of 4-(p-chlorophenyl)-4-methyl-2-pentynenitrile (18.5 g, 0.091 mol) in N,N-dimethylformamide, stirred at 80-85° C. for 4 hours, stirred at room temperature overnight and diluted with water. The aqueous mixture is extracted with ethyl acetate. The organic extracts are combined, washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo to obtain a residue. Column chromatography of the residue using silica gel and a 1:9 ethyl acetate/hexane solution gives the title product as an oil (15.6 g, 76.8% yield).

Workup

  1. stirringstirred at 80-85° C. for 4 hours
  2. stirringstirred at room temperature overnight
  3. extractionThe aqueous mixture is extracted with ethyl acetate
  4. washwashed with water
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customto obtain a residue

Sources & evidence

ORD record
ord-2b0d60a93a304d6594dc6d994d7e9ec7
Source dataset
uspto-grants-1999_12
Patent number
US05998673

Reaction notes

Loading…