1-Bromo-2-fluorobenzene → 2-(1-Dodecynyl)fluorobenzene

HRID 375930Notes

Reaction equation

HRID 375930 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[F:8].[CH:9]#[C:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]>[Cu]I.O1CCCC1>[C:9]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[F:8])#[C:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]

Participants

5

Reactant 2

HCID 612591-Bromo-2-fluorobenzeneHCID 698211-Dodecyne

Product 1

HCID 183730582-(1-Dodecynyl)fluorobenzeneYield 15%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
55 °C

Procedure

To a solution of 2-bromofluorobenzene (49 g), 1-dodecyne (210 ml) triethylamine (210 ml), and tetrahydrofuran (50 ml) was added (bis)triphenylphosphine palladium(II)chloride (532 mg) and copper(I)iodide (532 mg). The reaction mixture was warmed to 55° C. and stirred for 24 hr. The mixture was allowed to cool to room temperature and filtered. The precipitate was washed with ethyl acetate, and the filtrate was diluted with ethyl acetate and washed with water and brine. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated in vacuo. The residue was flash chromatographed over silica gel (eluted with hexane). The appropriate fractions were collected and evaporated. The residue was distilled to afford 11 g (15%) of product, bp 175°-180° C. at 1 mm Hg.

Workup

  1. temperatureto cool to room temperature
  2. filtrationfiltered
  3. washThe precipitate was washed with ethyl acetate
  4. additionthe filtrate was diluted with ethyl acetate
  5. washwashed with water and brine
  6. customThe organic phase was separated
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated in vacuo
  10. customchromatographed over silica gel (eluted with hexane)
  11. customThe appropriate fractions were collected
  12. customevaporated
  13. distillationThe residue was distilled

Sources & evidence

ORD record
ord-389556c90d7e4d66a6b16e801307b1fd
Source dataset
uspto-grants-1996_01
Patent number
US05488061

Reaction notes

Loading…