4-Bromo-1,2-difluorobenzene → HCID 54337969, compound

HRID 1109692Notes

Reaction equation

HRID 1109692 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([F:9])=[C:5]([F:10])[CH:4]=1.I[C:12]1[CH:17]=[CH:16][C:15]([CH:18]2[O:22][CH2:21][CH2:20][O:19]2)=[CH:14][CH:13]=1.C1(P(C2C=CC=CC=2)(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Pd](Cl)Cl.O1CCCC1>[F:10][C:5]1[CH:4]=[C:3]([C:12]2[CH:17]=[CH:16][C:15]([CH:18]3[O:19][CH2:20][CH2:21][O:22]3)=[CH:14][CH:13]=2)[CH:8]=[CH:7][C:6]=1[F:9]

Participants

7

Reactant 4

HCID 676754-Bromo-1,2-difluorobenzeneHCID 5462224MagnesiumHCID 14930739HCID 14930739, compoundHCID 178420557HCID 178420557, compound

Product 1

HCID 54337969HCID 54337969, compound

Reagents, catalysts & solvents 2

HCID 24290Palladium ChlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

A Grignard reagent solution prepared from 1.0 g of magnesium, 7.6 g of 1-bromo-3,4-difluorobenzene and 75 ml of tetrahydrofuran was added dropwise to a mixture of 9.0 g of 2-(p-iodophenyl)dioxolane, 100 ml of tetrahydrofuran, 0.025 g of palladium(II) chloride and 0.16 g of 1,3-bis(triphenylphosphino)propane. The reaction mixture was heated to boiling for 3 days and, after cooling, extracted with 200 ml of diethyl ether and 120 ml of 0.5N ammonium chloride solution. The organic phase was washed with three 80 ml portions of water, dried over sodium sulphate and concentrated. Chromatographic purification of the residue on silica gel with hexane/ethyl acetate (vol. 9:1) gave pure 2-(3',4'-difluoro-4-biphenylyl)dioxolane; m.p. 89°-91° C.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureafter cooling
  3. extractionextracted with 200 ml of diethyl ether and 120 ml of 0.5N ammonium chloride solution
  4. washThe organic phase was washed with three 80 ml portions of water
  5. dry with materialdried over sodium sulphate
  6. concentrationconcentrated
  7. customChromatographic purification of the residue on silica gel with hexane/ethyl acetate (vol. 9:1)

Sources & evidence

ORD record
ord-4b012a9c9d924672be387b3fff68f3c7
Source dataset
uspto-grants-1994_06
Patent number
US05322638

Reaction notes

Loading…