2-Methyl-3-butyn-2-ol → 4-(4-fluorophenyl)-2-methylbut-3-yn-2-ol

HRID 1648724Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][CH:3]=1.[OH:9][C:10]([CH3:14])([CH3:13])[C:11]#[CH:12].P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>C(N(CC)CC)C.[Pd].[Cu]I>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:12]#[C:11][C:10]([OH:9])([CH3:14])[CH3:13])=[CH:3][CH:4]=1

Participants

Conditions

Temperature: 70 °C

Procedure

To a solution of 35.2 g (0.19 mole) of 4-bromofluorobenzene and 25.2 g (0.3 mole) of 3-hydroxy-3-methyl-1-butine in 250 ml of triethylamine are added, under nitrogen, 1 g of the palladium complex PdCl2 [P(C6H5)3 ]2 and 0.2 g of copper(I) iodide. The reaction mixture is subsequently stirred for 24 hours at 70° C. After filtering off triethylammonium bromide and removing excess triethylamine by evaporation, the residue is taken up in 200 ml of ether and the solution is washed twice with 100 ml of 5% aqueous HCl solution and 100 ml of water, dried, treated with activated charcoal, and evaporated to dryness. The residue is chromatographed on silica gel with a 1:1 mixture of ether/hexane, affording 26.4 g (78%) of 1-fluoro-4-(3-hydroxy-3-methyl-1-butyn-1-yl)-benzene with a melting point of 124° C.

Workup

filtrationAfter filtering off triethylammonium bromide
customremoving excess triethylamine
customby evaporation
washthe solution is washed twice with 100 ml of 5% aqueous HCl solution and 100 ml of water
customdried
additiontreated with activated charcoal
customevaporated to dryness
customThe residue is chromatographed on silica gel with a 1:1 mixture of ether/hexane

Sources & evidence

ORD record: ord-2d038cce83ad48b49d4cff65137d7350
Source dataset: uspto-grants-1983_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04412856

Reaction notes

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