Sulfuric Acid → 5-(4-Fluorophenoxy)-1-penten-4-ol

HRID 1833477Notes

Reaction equation

HRID 1833477 reaction equation
[Mg].[CH2:2](Br)[CH:3]=[CH2:4].[F:6][C:7]1[CH:16]=[CH:15][C:10]([O:11][CH2:12][CH:13]=[O:14])=[CH:9][CH:8]=1.S(=O)(=O)(O)O>CCOCC.C(Br)C=C>[F:6][C:7]1[CH:16]=[CH:15][C:10]([O:11][CH2:12][CH:13]([OH:14])[CH2:4][CH:3]=[CH2:2])=[CH:9][CH:8]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 7841Allyl bromideHCID 5462224MagnesiumHCID 110518692-(4-Fluorophenoxy)acetaldehyde

Product 1

HCID 213175735-(4-Fluorophenoxy)-1-penten-4-olYield 77.2%

Reagents, catalysts & solvents 2

HCID 7841Allyl bromideCatalystHCID 3283Diethyl EtherSolvent4×

Procedure

To a mixture of ether (50 ml.) and magnesium turnings (4.49 g., 0.185 mole) is added a small amount of allyl bromide (ca. 0.5 g.). The mixture is stirred until Grignard reagent is formed (reflux of ether is a good sign). A solution of allyl bromide (24.2 g., 0.20 mole) and 4-fluorophenoxyacetaldehyde (19.0 g., 0.123 mole) in ether (110 ml.) is then added at such a rate as to maintain the reflux of ether. The resulting mixture is heated at reflux for another hour, cooled in an ice bath, and treated with dilute sulfuric acid (1.6 M, 70 ml.). The organic phase is separated and the aqueous phase is extracted with ether three times. The combined extracts are washed with 5% sodium bicarbonate, dried over anhydrous magnesium sulfate and finally concentrated on a rotary evaporator. The oil residue is vacuum distilled at 73° C./0.03 mm. to afford the desired product (18.6 g., 0.095 mole, 77%). ir (neat) 2.90, 3.22, 3.40, 6.05, 6.20, 6.62, 8.00, 8.25, 10.87, 12.10, 13.14μ; pmr (CCl4)δ2.32 (2H, t, J=6Hz), 2.54 (1H, m), 3.6-4.1 (3H, m), 4.8-5.05(1H, m), 5.05-5.25 (1H, m), 5.4-6.3 (1H, m), 6.6-7.1 (4H, m).

Workup

  1. customis formed (
  2. temperatureto maintain the
  3. temperatureThe resulting mixture is heated
  4. temperatureat reflux for another hour
  5. temperaturecooled in an ice bath
  6. customThe organic phase is separated
  7. extractionthe aqueous phase is extracted with ether three times
  8. washThe combined extracts are washed with 5% sodium bicarbonate
  9. dry with materialdried over anhydrous magnesium sulfate
  10. concentrationfinally concentrated on a rotary evaporator
  11. distillationdistilled at 73° C./0.03 mm

Sources & evidence

ORD record
ord-92367ea8702a4ce1a7ddf34677da3bc5
Source dataset
uspto-grants-1978_01
Patent number
US04066675

Reaction notes

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