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

HRID 867095Notes

Reaction equation

HRID 867095 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 77.1%

Reagents, catalysts & solvents 2

HCID 7841Allyl bromideCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

Allyl bromide (~0.5 g.) is added to a stirred suspension of magnesium turnings (4.49 g., 0.185 mole) in dry ether (50 ml.) at 25° C. Upon initiation of reflux, the reaction suspension is stirred and treated with a solution of allyl bromide (24.2 g., 0.2 mole) and 4-fluorophenoxyacetaldehyde (19 g., 0.123 mole) in dry ether (110 ml.) added at such a rate as to maintain a gentle reflux. The resulting reaction mixture is heated at reflux for 1 hour, cooled to 0°-5° C., and treated with 3.2 N sulfuric acid (70 ml.), providing a heterogeneous mixture. After separating the phases, the aqueous phase is extracted with ether three times. The organic phase is combined with the ethereal extracts and washed with 5% aqueous sodium bicarbonate, dried over magnesium sulfate, and filtered. Evaporation of the filtrate in vacuo affords an oily residue which is distilled to provide the title compound as a colorless oil (18.6 g., 77%), bp0.03 73° C.; pmr (CCl4) δ2.32 (2H, t), 2.54 (H, m) 3.6-4.1 (3H, m), 4.8-5.05 (H, m) 5.05-5.25 (H, m), 5.4-6.3 (H, m) and 6.6-7.1 (4H, m).

Workup

  1. temperatureUpon initiation of reflux
  2. additionadded at such a rate as
  3. temperatureto maintain a gentle reflux
  4. customThe resulting reaction mixture
  5. temperatureis heated
  6. temperatureat reflux for 1 hour
  7. temperaturecooled to 0°-5° C.
  8. customproviding a heterogeneous mixture
  9. customAfter separating the phases
  10. extractionthe aqueous phase is extracted with ether three times
  11. washwashed with 5% aqueous sodium bicarbonate
  12. dry with materialdried over magnesium sulfate
  13. filtrationfiltered
  14. customEvaporation of the filtrate in vacuo
  15. customaffords an oily residue which
  16. distillationis distilled

Sources & evidence

ORD record
ord-3cd3ecbfba2b4502ae0bfe32bb394e27
Source dataset
uspto-grants-1978_07
Patent number
US04102888

Reaction notes

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