Tetrahydrofuran → 2-(1-Undecynyl)fluorobenzene

HRID 1899446Notes

Reaction equation

HRID 1899446 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][CH3:19].O1CCCC1.C(N(CC)CC)C>C(OCC)(=O)C.[Cu]I>[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][CH3:19]

Participants

7

Reactant 4

HCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 612591-Bromo-2-fluorobenzene2×HCID 752491-Undecyne

Product 1

HCID 183730212-(1-Undecynyl)fluorobenzeneYield 53.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
55 °C

Procedure

To a solution of 2-bromofluorobenzene (17.5 g), 1-undecyne (18.3 g), tetrahydrofuran (50 ml), and triethylamine (70 ml) was added bistriphenylphosphine palladium(II)chloride (1.2 g) and copper(I) iodide (162 mg). The reaction mixture was stirred at 55° C. for 3 hr, and an additional 2-bromofluorobenzene (2.0 g) and bistriphenylphosphine palladium(II)chloride (200 mg) were added. The mixture was stirred at 55° C. overnight, allowed to cool to room temperature, diluted with ethyl acetate and washed with water. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated in vacuo. The residue was chromatographed over silica gel (eluted with hexane). The appropriate fractions were collected and evaporated. The residue was distilled twice under vacuum to give 13.1 g (53%) of product.

Workup

  1. stirringThe mixture was stirred at 55° C. overnight
  2. temperatureto cool to room temperature
  3. washwashed with water
  4. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe residue was chromatographed over silica gel (eluted with hexane)
  8. customThe appropriate fractions were collected
  9. customevaporated
  10. distillationThe residue was distilled twice under vacuum

Sources & evidence

ORD record
ord-b1c69530f1d64944841fbc68c68f57ee
Source dataset
uspto-grants-1996_11
Patent number
US05571923

Reaction notes

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