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

HRID 743795Notes

Reaction equation

HRID 743795 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]>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

4

Reactant 2

HCID 612591-Bromo-2-fluorobenzeneHCID 698211-Dodecyne

Product 1

HCID 183730582-(1-Dodecynyl)fluorobenzeneYield 15%

Reagents, catalysts & solvents 1

HCID 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(l)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-4368410e2082477cac7c3940ed888403
Source dataset
uspto-grants-1996_09
Patent number
US05557006

Reaction notes

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