Hydrochloric Acid → methyl 3-(4-methylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylate

HRID 1169320Notes

Reaction equation

HRID 1169320 reaction equation
[CH3:1][C:2]1[CH:21]=[CH:20][C:5]([CH2:6][O:7][C:8]2[CH:19]=[CH:18][C:11]3[CH2:12][CH2:13][CH2:14][CH2:15][C:16](=[O:17])[C:10]=3[CH:9]=2)=[CH:4][CH:3]=1.C[O-].[Na+].Cl.[C:26](=O)([O:29]C)[O:27][CH3:28]>>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][O:7][C:8]2[CH:19]=[CH:18][C:11]3[CH2:12][CH2:13][CH2:14][CH:15]([C:26]([O:27][CH3:28])=[O:29])[C:16](=[O:17])[C:10]=3[CH:9]=2)=[CH:20][CH:21]=1

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 12021Dimethyl CarbonateHCID 10942334Sodium MethoxideHCID 22990062HCID 22990062, compound

Product 1

HCID 22990087methyl 3-(4-methylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylateYield 88%

Conditions

Temperature
110 °C

Procedure

To 3-(4-methylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene (2.67 g, 9.52 mmol) dissolved in dimethyl carbonate (40 ml) was added sodium methoxide (2.57 g, 47.6 mmol), and the resulting mixture was stirred at reflux with heating (110° C.) for 6 hours. The reaction mixture was mixed with 1 N hydrochloric acid (60 ml) under ice cooling and was concentrated under reduced pressure to remove the organic solvent, and then the aqueous layer was extracted with ethyl acetate (30 ml×3). The combined organic layers were dried with anhydrous magnesium sulfate and were then concentrated under reduced pressure, and the residue was subjected to column chromatography (silica gel: 40 g, ethyl acetate/hexane=1/30). The objective fractions were concentrated under reduced pressure to obtain methyl 3-(4-methylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylate (2.84 g, 8.39 mmol, 88%).

Workup

  1. temperatureat reflux
  2. concentrationwas concentrated under reduced pressure
  3. customto remove the organic solvent
  4. extractionthe aqueous layer was extracted with ethyl acetate (30 ml×3)
  5. dry with materialThe combined organic layers were dried with anhydrous magnesium sulfate
  6. concentrationwere then concentrated under reduced pressure
  7. concentrationThe objective fractions were concentrated under reduced pressure

Sources & evidence

ORD record
ord-c265f7205f544f979fa75dbb6d141209
Source dataset
uspto-grants-2003_09
Patent number
US06627651B1

Reaction notes

Loading…