Cesium fluoride → 5-Allyl-1,2-difluoro-3-methoxybenzene

HRID 453407Notes

Reaction equation

HRID 453407 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([F:10])=[C:4]([F:11])[CH:3]=1.[CH2:12](B([O-])OC(C(C)(C)C)C)[CH:13]=[CH2:14].[F-].[Cs+]>O1CCCC1.C(OCC)C.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]([C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([F:10])=[C:4]([F:11])[CH:3]=1)[CH:13]=[CH2:12]

Participants

7

Reactant 3

HCID 25953Cesium fluorideHCID 27732885-Bromo-1,2-difluoro-3-methoxybenzeneHCID 86657601Pinacolyl allylboronate

Product 1

HCID 552648935-Allyl-1,2-difluoro-3-methoxybenzene

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

3.06 g of 1-bromo-3,4-difluoro-5-methoxybenzene (D2), 4.54 ml of pinacolyl allylboronate, 3.04 g of tetrakis(triphenylphosphine)palladium(0) and 7.62 g of caesium fluoride are suspended in 115 ml of tetrahydrofuran under an argon atmosphere. The reaction mixture is subsequently heated under reflux for 48 h. For work-up, the mixture is diluted with 400 ml of diethyl ether and extracted with 100 ml of water and 100 ml of saturated NaCl solution. The combined organic phases are dried over Na2SO4, filtered and evaporated to dryness in vacuo. The residue is purified by flash column chromatography on silica gel (solvent: cyclohexane), giving 1.59 g of the title compound as a colourless oil; MS: 184.0 (M+); TLC: Rf=0.69 (cyclohexane/ethyl acetate 8:1 parts by volume).

Workup

  1. temperatureThe reaction mixture is subsequently heated
  2. temperatureunder reflux for 48 h
  3. extractionextracted with 100 ml of water and 100 ml of saturated NaCl solution
  4. dry with materialThe combined organic phases are dried over Na2SO4
  5. filtrationfiltered
  6. customevaporated to dryness in vacuo
  7. customThe residue is purified by flash column chromatography on silica gel (solvent: cyclohexane)

Sources & evidence

ORD record
ord-ce6f1d4b78b64bd68343e439c71486af
Source dataset
uspto-grants-2013_07
Patent number
US08492440B2

Reaction notes

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