Allyl Alcohol → HCID 22336194, compound

HRID 1167199Notes

Reaction equation

HRID 1167199 reaction equation
C(O)C=C.[CH3:5][CH2:6][Mg+].[Br-].[CH2:9]([C:12]1[C:17]2[C:18](=[O:24])[O:19][C:20](C)(C)[O:21][C:16]=2[CH:15]=[CH:14][CH:13]=1)[CH:10]=[CH2:11].[NH4+].[Cl-]>C1COCC1.O.C(OCC)C>[CH2:9]([C:12]1[C:17]([C:18]([O:19][CH2:20][CH:6]=[CH2:5])=[O:24])=[C:16]([OH:21])[CH:15]=[CH:14][CH:13]=1)[CH:10]=[CH2:11]

Participants

8

Reactant 4

HCID 7858Allyl AlcoholHCID 25517Ammonium ChlorideHCID 111486725-allyl-2,2-dimethyl-benzo[1,3]dioxin-4-oneHCID 178461630HCID 178461630, compound

Product 1

HCID 22336194HCID 22336194, compoundYield 92.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of allyl alcohol (2.25 mL, 32.8 mL) in THF (10 mL) was added dropwise EtMgBr (1.0M in THF, 29.8 mmol) at 0° C. After stirring for 15 min at rt, a solution of 5-allyl-2,2-dimethyl-benzo[1,3dioxin-4-one (iv) (1.3 g, 5.96 mmol) in THF (5 mL) was added and stirring was continued for 5 h at rt and 2.5 h at 60° C. Diethyl ether (50 mL) was added and the mixture was poured into saturated aqueous NH4Cl (20 mL) and water (50 mL). An extraction was performed with Et2O (3×) and the combined organics were dried over MgSO4 and concentrated in vacuo. The residue was purified by FC (2% Et2O/pentane) to give 1.2 g of allyl 6-allyl-2-hydroxybenzoate (v) (90%) as a colorless oil. v: IR 2918, 2850, 1663, 1607, 1450, 1248, 1219, 909, 733 cm−1; 1H NMR (400 MHz, CDCl3) δ 7.33 (1H, app.t, J=7.3 Hz), 6.88 (1H, br d, J=7.3 Hz), 6.75 (1H, d, J=7.3 Hz), 5.92-6.09 (2H, m), 5.43 (1H, br d, J=14.0 Hz), 5.33 (1H, br d, J=8.3 Hz), 5.02 (1H, br d, J=10.0 Hz), 4.96 (1H, br d, J=1.65 Hz), 4.86 (2H, br d, J=6.7 Hz), 3.70 (2H, d, J=5.9 Hz); 13C NMR (75 MHz, CDCl3) δ 171.0, 162.8, 143.0, 137.7, 134.6, 131.5, 122.6, 119.8, 116.3, 115.6, 112.2, 66.7, 40.6; MS (EI) 218 (M+, 10), 177 (24), 159 (100).

Workup

  1. stirringstirring
  2. waitwas continued for 5 h at rt and 2.5 h at 60° C
  3. extractionAn extraction
  4. dry with materialthe combined organics were dried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by FC (2% Et2O/pentane)

Sources & evidence

ORD record
ord-d7eada145d87469b9b726d07263db23a
Source dataset
uspto-grants-2003_09
Patent number
US06617348B1

Reaction notes

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