Acetic Acid → Methyl 6-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate

HRID 35663

Reaction equation

HRID 35663 reaction equation
[H-].[Na+].[C:3](=[O:8])([O:6][CH3:7])OC.[CH3:9][O:10][C:11]1[CH:12]=[C:13]2[C:18](=[CH:19][CH:20]=1)[C:17](=[O:21])[CH2:16][CH2:15][CH2:14]2.C(O)(=O)C>O1CCCC1>[CH3:9][O:10][C:11]1[CH:12]=[C:13]2[C:18](=[CH:19][CH:20]=1)[C:17](=[O:21])[CH:16]([C:3]([O:6][CH3:7])=[O:8])[CH2:15][CH2:14]2

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 12021Dimethyl CarbonateHCID 141126-Methoxy-alpha-tetraloneHCID 24758Sodium hydride

Product 1

HCID 12364403Methyl 6-methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylateYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A suspension of 24.0 g (0.60 mole) of sodium hydride (60% dispersion in mineral oil) and 49.5 ml (52.9 g; 0.59 mole) of dimethyl carbonate (freshly distilled from sodium hydride) in 240 ml of tetrahydrofuran under a nitrogen atmosphere was stirred and heated to reflux. Reflux was maintained while a solution of 29.7 g (0.17 mole) of 6-methoxy-1-tetralone in 105 ml of tetrahydrofuran was added dropwise over two hours. After addition was complete, the mixture was stirred at reflux for an additional 90 minutes, cooled in ice, and treated dropwise with 36 ml of glacial acetic acid, followed by 450 ml of ice water. The two-phase reaction mixture was extracted with ethyl acetate (4×250 ml), and the combined organic layers were washed with water (1×600 ml), 5% aqueous sodium bicarbonate solution (3×600 ml), and water again. The ethyl acetate extract was dried (anhydrous sodium sulfate and evaporated (vacuum). The residue was pulverized and stirred in 500 ml of hexane. Filtration yielded 37.9 g (96% yield) of the ester product, mp 79°-81°, suitable for further synthesis. A sample purified by bulb-to-bulb distillation followed by recrystallization from hexane/ethyl acetate was analytically pure, mp 82°-84° (a mp of 88°-89° is given by J. Jacques and A. Horeau, Bull. Soc. Chem. France, 512 (1950)).

Workup

  1. distillationfreshly distilled from sodium hydride) in 240 ml of tetrahydrofuran under a nitrogen atmosphere
  2. temperatureheated to reflux
  3. temperatureReflux
  4. additionwas added dropwise over two hours
  5. additionAfter addition
  6. stirringthe mixture was stirred
  7. temperatureat reflux for an additional 90 minutes
  8. temperaturecooled in ice
  9. customThe two-phase reaction mixture
  10. extractionwas extracted with ethyl acetate (4×250 ml)
  11. washthe combined organic layers were washed with water (1×600 ml), 5% aqueous sodium bicarbonate solution (3×600 ml), and water again
  12. extractionThe ethyl acetate extract
  13. dry with materialwas dried (anhydrous sodium sulfate
  14. customevaporated (vacuum)
  15. stirringstirred in 500 ml of hexane
  16. filtrationFiltration

Sources & evidence

ORD record
ord-ebf14da204324fc1927bfd9e9d635b94
Source dataset
uspto-grants-1988_08
Patent number
US04767776

Linked notes

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