Stannane, tributyl(1-ethoxyethenyl)- → 4-Acetyl-2-fluorobenzonitrile

HRID 1436420Notes

Reaction equation

HRID 1436420 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1.C([Sn](CCCC)(CCCC)[C:16]([O:18]CC)=[CH2:17])CCC>C1(C)C=CC=CC=1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:16]([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1)(=[O:18])[CH3:17]

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 7360294-Bromo-2-fluorobenzonitrile

Product 1

HCID 224816534-Acetyl-2-fluorobenzonitrileYield 11.6%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 4-bromo-2-fluorobenzonitrile (10.6 g, 52.8 mmol), tributyl(1-ethoxyvinyl)tin (21 g, 58.1 mmol), and trans-dichlorobis(triphenylphosphine)palladium (II) (371 mg, 0.53 mmol) in 190 mL of dry toluene were refluxed for 2 h and then quenched with 5% HCl and stirred for 30 min. Ethyl acetate was added and the layers were separated. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give 6.5 g of crude product. Purification of the product on silica gel using 5% ethyl acetate:hexane gave 4-acetyl-2-fluorobenzonitrile (1.0 g, 11%), MS (ES) m/z 164 [M+H]+.

Workup

  1. temperaturewere refluxed for 2 h
  2. customquenched with 5% HCl
  3. additionEthyl acetate was added
  4. customthe layers were separated
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto give 6.5 g of crude product
  9. customPurification of the product on silica gel using 5% ethyl acetate

Sources & evidence

ORD record
ord-45d16bef3c5945e3bf87a91b22ed8350
Source dataset
uspto-grants-2009_11
Patent number
US07618990B2

Reaction notes

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