Phenol → 3-methoxy-4-(2-propenyloxy) benzenemethanol

HRID 1260134Notes

Reaction equation

HRID 1260134 reaction equation
[CH2:1]([OH:11])[C:2]1[CH:10]=[CH:9][C:7]([OH:8])=[C:4]([O:5][CH3:6])[CH:3]=1.[CH2:12](Br)[CH:13]=[CH2:14].C(=O)([O-])[O-].[K+].[K+].C1(O)C=CC=CC=1>CC(C)=O.C(Cl)Cl.CCOC(C)=O.O>[CH3:6][O:5][C:4]1[CH:3]=[C:2]([CH2:1][OH:11])[CH:10]=[CH:9][C:7]=1[O:8][CH2:14][CH:13]=[CH2:12]

Participants

9

Reactant 4

HCID 996PhenolHCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 62348Vanillyl alcohol

Product 1

HCID 19453853-methoxy-4-(2-propenyloxy) benzenemethanolYield 94.8%

Reagents, catalysts & solvents 4

HCID 180AcetoneSolvent2×HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

Acetone (107.5 mL), vanillyl alcohol (25 g, 0.163 mol), and allyl bromide (15.8 mL, 0.183 mol) were added to a 250 mL, round-bottomed flask and stirred until homogeneous. Potassium carbonate (22.5 g, 0.163 mol) was then added slowly, which briefly gave a light pink color that indicated deprotonation of the phenol. The mixture was heated at 60° C. overnight. The reaction was monitored by TLC using 10% acetone in CH2Cl2 as eluent. Upon completion, the reaction mixture was allowed to cool to rt with stirring. The acetone was removed under vacuum, yielding a white residue. CH2Cl2 (200 mL) and H2O (200 mL) were added to redissolve the residue and transferred to a separatory funnel. The aqueous layer was removed and the organic layer was washed with 1 M NaOH (3×100 mL) and saturated NaCl (1×100 mL). The organic layer was then collected, dried over MgSO4. After filtration, the solvent was removed under vacuum to afford a yellow powder. The yellow powder was redissolved in EtOAc (250 mL), which was subsequently removed under vacuum (in order to remove excess allyl bromide) to afford the product as a fine, white powder (30.0 g, 93% yield). 1H NMR δ=6.94 (s, 1H), 6.86 (s, 2H), 6.09 (multi, 1H), 5.42 (dd, J1=20, J2=1.5, 1H), 5.30 (dd, J1=20, J2=1.5, 1H), 4.63 (d, J=3.6, 2H), 4.62 (d, J=5, 2H), 3.89 (s, 3H), 1.57 (t, J=6, 1H).

Workup

  1. customwhich briefly gave a light pink color that
  2. temperatureto cool to rt
  3. stirringwith stirring
  4. customThe acetone was removed under vacuum
  5. customyielding a white residue
  6. dissolutionto redissolve the residue
  7. customtransferred to a separatory funnel
  8. customThe aqueous layer was removed
  9. washthe organic layer was washed with 1 M NaOH (3×100 mL) and saturated NaCl (1×100 mL)
  10. customThe organic layer was then collected
  11. dry with materialdried over MgSO4
  12. filtrationAfter filtration
  13. customthe solvent was removed under vacuum
  14. customto afford a yellow powder
  15. customwhich was subsequently removed under vacuum (in order to remove excess allyl bromide)

Sources & evidence

ORD record
ord-0718533a246140e294cf36e04dede4a4
Source dataset
uspto-grants-2013_06
Patent number
US08470587B2

Reaction notes

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