Potassium Fluoride → 4-(1-Ethoxyvinyl)-2-fluoro-3-pyridinecarbaldehyde

HRID 47354

Reaction equation

HRID 47354 reaction equation
[F:1][C:2]1[C:7]([CH:8]=[O:9])=[C:6](I)[CH:5]=[CH:4][N:3]=1.[CH2:11]([O:13][C:14]([Sn](CCCC)(CCCC)CCCC)=[CH2:15])[CH3:12].[F-].[K+]>O1CCOCC1.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>[CH2:14]([O:13][C:11]([C:6]1[CH:5]=[CH:4][N:3]=[C:2]([F:1])[C:7]=1[CH:8]=[O:9])=[CH2:12])[CH3:15]

Participants

6

Reactant 3

HCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 99923282-Fluoro-4-iodopyridine-3-carbaldehyde

Product 1

HCID 227450184-(1-Ethoxyvinyl)-2-fluoro-3-pyridinecarbaldehyde

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

There are mixed in succession 8 g (31.9 mmol) of 2-fluoro-4-iodo-3-pyridinecarbaldehyde (described in J.O.C, 1993, 58, pp. 7832), 12.7 g (35.96 mmol) of 1-ethoxyvinyltributyltin and 740 mg of tetrakis(triphenylphosphine)palladium (2% molar) in 280 ml of dioxane. The reaction mixture is heated at reflux until the starting material has disappeared completely. After returning to room temperature a solution of potassium fluoride is added to the reaction mixture. Vigorous stirring is maintained for 10 minutes in order to cause precipitation of the tributyltin fluoride, which is filtered off. The filtrate is plunged into a sodium chloride solution. The aqueous phase is extracted 3 times with dichloromethane and then the organic phases are combined, dried over magnesium sulphate, concentrated and purified by chromatography over a silica column, using a dichloromethane/cyclohexane mixture (95/5) as eluant to yield the expected product.

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureat reflux until the starting material
  3. customAfter returning to room temperature
  4. additionis added to the reaction mixture
  5. temperatureis maintained for 10 minutes in order
  6. customprecipitation of the tributyltin fluoride, which
  7. filtrationis filtered off
  8. extractionThe aqueous phase is extracted 3 times with dichloromethane
  9. dry with materialdried over magnesium sulphate
  10. concentrationconcentrated
  11. custompurified by chromatography over a silica column

Sources & evidence

ORD record
ord-b1911e1b043043799444f39d04e81d1e
Source dataset
uspto-grants-2004_03
Patent number
US06699876B2

Linked notes

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