4-Hydroxybenzoic Acid → 4-(Prop-2-en-1-yloxy)benzoic acid

HRID 2394513Notes

Reaction equation

HRID 2394513 reaction equation
[OH:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][CH:3]=1.CO.[OH-].[K+].[CH2:15](Br)[CH:16]=[CH2:17]>O>[CH2:17]([O:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][CH:3]=1)[CH:16]=[CH2:15]

Participants

6

Reactant 4

HCID 1354-Hydroxybenzoic AcidHCID 887MethanolHCID 7841Allyl bromideHCID 14797Potassium Hydroxide

Product 1

HCID 4606904-(Prop-2-en-1-yloxy)benzoic acid

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
25 °C

Procedure

4-(2-Propenyloxy)benzoic acid was synthesized by Apfel's method (Apfel et al, Anal. Chem., 1985, 57, 651-658). A 1 L three-neck round-bottom flask was equipped with a condenser, 150 mL additional funnel, heating bath, and magnetic stirrer. 90 g (0.65 mol) of 4-hydroxybenzoic acid and 400 mL of methanol were added at 25° C. and stirred. After the acid was dissolved, 105 g (1.9 mol) of potassium hydroxide in 125 mL of distilled water was added dropwise. The reaction mixture was heated to reflux, and 90 g (0.74 mol) of allyl bromide was then added over a 2 hour period. The reaction mixture was allowed to reflux for 8 hours. As the reaction proceeded, potassium bromide precipitated. From this mixture, 250 mL of methanol was removed by evaporation. The remainder of the reaction mixture was cooled to 25° C. and then added to 2.5 L of distilled water. Hexane (250 mL) was added to extract organic impurities. After discarding the organic phase, the aqueous phase was heated to 40° C. and neutralized with 300 mL of 20% HCl. The crude product precipitated during the neutralization, was subsequently collected by filtration and purified by recrystallization from ethanol. Yield: 46 g (40.2%), mp 165° C.

Workup

  1. customA 1 L three-neck round-bottom flask was equipped with a condenser, 150 mL additional funnel
  2. temperatureheating bath, and magnetic stirrer
  3. dissolutionAfter the acid was dissolved
  4. temperatureThe reaction mixture was heated
  5. temperatureto reflux
  6. temperatureto reflux for 8 hours
  7. custompotassium bromide precipitated
  8. customFrom this mixture, 250 mL of methanol was removed by evaporation
  9. additionadded to 2.5 L of distilled water
  10. additionHexane (250 mL) was added
  11. extractionto extract organic impurities
  12. temperaturethe aqueous phase was heated to 40° C. and neutralized with 300 mL of 20% HCl
  13. customThe crude product precipitated during the neutralization
  14. filtrationwas subsequently collected by filtration
  15. custompurified by recrystallization from ethanol

Sources & evidence

ORD record
ord-e6059c01239f431d945684527ec02a52
Source dataset
uspto-grants-1998_09
Patent number
US05811504

Reaction notes

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