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

HRID 1977707Notes

Reaction equation

HRID 1977707 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-70d2c4993ec342b99830239e217e7f0e
Source dataset
uspto-grants-2001_05
Patent number
US06235754B1

Reaction notes

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