Benzoic acid 1-cyano-3-(4-methoxyphenyl)-allyl ester → 4-(4-Methoxyphenyl)but-3-enenitrile

HRID 48131Notes

Reaction equation

HRID 48131 reaction equation
[C:1]([CH:3](OC(=O)C1C=CC=CC=1)[CH:4]=[CH:5][C:6]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][CH:7]=1)#[N:2]>O1CCCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:13][O:12][C:9]1[CH:10]=[CH:11][C:6]([CH:5]=[CH:4][CH2:3][C:1]#[N:2])=[CH:7][CH:8]=1

Participants

4

Reactant 1

HCID 54392804Benzoic acid 1-cyano-3-(4-methoxyphenyl)-allyl ester

Product 1

HCID 544351994-(4-Methoxyphenyl)but-3-enenitrileYield 57%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Benzoic acid 1-cyano-3-(4-methoxy-phenyl)-allyl ester (15 g; ca 0.050 mol) is dissolved in 100 ml of anhydrous tetrahydrofuran. Tetrakis(triphenylphosphine)palladium (0.88 g; 0.8 mmol) and 4.8 ml of poly(methylhydrosiloxane) (ca 80 meq; Aldrich) are added, and the mixture is stirred at ca 20° C., cooling with a cold water bath. After 3 h 30 min, the mixture is concentrated by rotary evaporation, stirred with 150 ml of water to hydrolyze the siloxane. The polymer and organic materials are redissolved in CH2Cl2 and washed with saturated sodium bicarbonate to remove benzoic acid. Evaporation of the solvent and flash chromatography (150 g SiO2; hexane:ethyl acetate 80:20 v:v) affords 4.9 g (57%) of pure 4-(4-methoxy-phenyl)-but-3-enenitrile, mp 75-76° C.

Workup

  1. temperaturecooling with a cold water bath
  2. concentrationthe mixture is concentrated by rotary evaporation
  3. stirringstirred with 150 ml of water
  4. dissolutionThe polymer and organic materials are redissolved in CH2Cl2
  5. washwashed with saturated sodium bicarbonate
  6. customto remove benzoic acid
  7. customEvaporation of the solvent and flash chromatography (150 g SiO2; hexane:ethyl acetate 80:20 v:v)

Sources & evidence

ORD record
ord-0ab9cabf15834044aea6d28280ea2ec8
Source dataset
uspto-grants-2004_03
Patent number
US06703182B1

Reaction notes

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