Acetic Acid → Methyl 2-acetyl-3,5-diallyloxyphenylacetate

HRID 495180

Reaction equation

HRID 495180 reaction equation
[CH2:1]([O:4][C:5]1[CH:6]=[C:7]([CH2:15][C:16]([O:18][CH3:19])=[O:17])[CH:8]=[C:9]([O:11][CH2:12][CH:13]=[CH2:14])[CH:10]=1)[CH:2]=[CH2:3].[C:20](O)(=[O:22])[CH3:21].FC(F)(F)C(OC(=O)C(F)(F)F)=O.C(=O)([O-])O.[Na+]>FC(F)(F)C(O)=O>[C:20]([C:8]1[C:9]([O:11][CH2:12][CH:13]=[CH2:14])=[CH:10][C:5]([O:4][CH2:1][CH:2]=[CH2:3])=[CH:6][C:7]=1[CH2:15][C:16]([O:18][CH3:19])=[O:17])(=[O:22])[CH3:21]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 9845Trifluoroacetic anhydrideHCID 516892Sodium BicarbonateHCID 23116191Methyl 3,5-diallyloxyphenylacetate

Product 1

HCID 68421776Methyl 2-acetyl-3,5-diallyloxyphenylacetateYield 70.4%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Conditions

Temperature
4 °C

Procedure

Methyl 3,5-diallyloxyphenylacetate (40 g, 0.14 mol) obtained in Example 5, Step 1 was dissolved in trifluoroacetic acid (0.15 L). After the solution was cooled to 4° C., acetic acid (9.5 mL, 0.17 mol) and trifluoroacetic anhydride (40 mL, 0.28 mol) were added thereto, followed by stirring at 4° C. for 3.5 hours. The reaction mixture was gradually added to a saturated aqueous solution of sodium hydrogencarbonate for neutralization, followed by extraction with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/20-1/6) to obtain methyl 2-acetyl-3,5-diallyloxyphenylacetate (30 g, 65%). 1H-NMR (CDCl3, 300 MHz) δ (ppm): 6.43 (d, J=2.2 Hz, 1H), 6.37 (d, J=2.2 Hz, 1H), 6.07-5.98 (m, 2H), 5.44-5.27 (m, 4H), 4.57-4.52 (m, 4H), 3.69 (s, 2H), 3.68 (s, 3H), 2.53 (s, 3H)

Workup

  1. extractionfollowed by extraction with ethyl acetate
  2. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/20-1/6)

Sources & evidence

ORD record
ord-d7b2a0324f5548dfb1e51811df6fdf0b
Source dataset
uspto-grants-2009_05
Patent number
US07538224B2

Linked notes

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