Sulfuric Acid → 1-(4-Methoxyphenyl)butane-1,3-dione

HRID 887047

Reaction equation

HRID 887047 reaction equation
[C:1](OCC)(=[O:3])[CH3:2].[H-].[Na+].[CH3:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17](=[O:19])[CH3:18])=[CH:13][CH:12]=1.S(=O)(=O)(O)O>C1COCC1.C(O)C.C1OCCOCCOCCOCCOCCOC1>[CH3:9][O:10][C:11]1[CH:16]=[CH:15][C:14]([C:17](=[O:19])[CH2:18][C:1](=[O:3])[CH3:2])=[CH:13][CH:12]=1

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 74764'-MethoxyacetophenoneHCID 8857Ethyl AcetateHCID 24758Sodium hydride

Product 1

HCID 776401-(4-Methoxyphenyl)butane-1,3-dioneYield 60.5%

Reagents, catalysts & solvents 3

HCID 702EthanolCatalystHCID 2855718-Crown-6CatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

To 9.80 mL of ethyl acetate (100 mmol) in 40 mL dry THF at room temperature was added 2.0 g of 60% sodium hydride (49.9 mmol), 7.50 g of 4′-methoxyacetophenone (49.9 mmol), 100.0 mg of 18-crown-6 (0.40 mmol), and 2 drops of ethanol. After 30 minutes, the reaction was refluxed for 1 h, and then 100 mL of dry THF was added. After an additional 1 h, 30 mL THF was added. After 1 h the reaction was cooled to 0° C. and 25 mL of 10% aqueous sulfuric acid was added. The product was extracted with diethyl ether. The ether extracts were dried with Na2SO4, filtered, and concentrated in vacuo. The crude material was purified via silica gel chromatography eluting with 4:1 hexane:ethyl acetate to give 5.8 g of 1-(4-methoxyphenyl)butane-1,3-dione containing 30% starting material (via 1H NMR 42% yield).

Workup

  1. temperaturethe reaction was refluxed for 1 h
  2. waitAfter an additional 1 h
  3. extractionThe product was extracted with diethyl ether
  4. dry with materialThe ether extracts were dried with Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified via silica gel chromatography
  8. washeluting with 4:1 hexane

Sources & evidence

ORD record
ord-daa254d9fbe14efb946f262df292762e
Source dataset
uspto-grants-2012_08
Patent number
US08247414B2

Linked notes

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