Diethyl Ether → 4-(4-Fluorophenoxy)-1-butyn-3-one

HRID 1354488Notes

Reaction equation

HRID 1354488 reaction equation
[C:1]([Mg]Br)#[CH:2].CON(C)[C:8](=[O:18])[CH2:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([F:17])=[CH:13][CH:12]=1.CCOCC>C1COCC1>[F:17][C:14]1[CH:13]=[CH:12][C:11]([O:10][CH2:9][C:8](=[O:18])[C:1]#[CH:2])=[CH:16][CH:15]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 226078882-(4-fluorophenoxy)-N-methoxy-N-methylacetamideHCID 178418486HCID 178418486, compound

Product 1

HCID 226078934-(4-Fluorophenoxy)-1-butyn-3-oneYield 209.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of ethynylmagnesium bromide (0.5 M in THF, 508 mL, 254 mmol), was added slowly, as a stream down the side of the flask, to an ice water cooled solution of N-methoxy-N-methyl-2-(4-fluorophenoxy)ethanamide (20.00 g, 74 mmol) in THF (100 mL). After an additional 30 minutes at 0° C., the reaction mixture was poured into a vigorously stirred mixture of 1M NaH2SO4 (1700 mL) and ether (1 L). The layers were separated and the aqueous layer then extracted with ether (700 mL). The combined organic phases were washed with brine and dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by eluting through a plug of silica gel (10 cm×3 cm) with 1:4 ether:pet. ether to afford 27.65 g (91% yield) of 4-(4-fluorophenoxy)-1-butyn-3-one, a compound of formula (AA), as a low melting solid; 1H NMR (CDCl3) δ 3.40 (s, 1H), 4.70 (s, 2H), 6.85 (m, 2H), 7.0 (t, 2H) ppm.

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer then extracted with ether (700 mL)
  3. washThe combined organic phases were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe residue was purified
  8. washby eluting through a plug of silica gel (10 cm×3 cm) with 1:4 ether

Sources & evidence

ORD record
ord-c99745c0e255497e9a17b53bc52aed0f
Source dataset
uspto-grants-2007_05
Patent number
US07223798B2

Reaction notes

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