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

HRID 1169324Notes

Reaction equation

HRID 1169324 reaction equation
[C:1]1([C:7]2[CH:26]=[CH:25][C:10]([CH2:11][O:12][C:13]3[CH:24]=[CH:23][C:16]4[CH2:17][CH2:18][CH2:19][CH2:20][C:21](=[O:22])[C:15]=4[CH:14]=3)=[CH:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[O-].[Na+].Cl.[C:31](=O)([O:34]C)[O:32][CH3:33]>>[C:1]1([C:7]2[CH:8]=[CH:9][C:10]([CH2:11][O:12][C:13]3[CH:24]=[CH:23][C:16]4[CH2:17][CH2:18][CH2:19][CH:20]([C:31]([O:32][CH3:33])=[O:34])[C:21](=[O:22])[C:15]=4[CH:14]=3)=[CH:25][CH:26]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 12021Dimethyl CarbonateHCID 10942334Sodium MethoxideHCID 229899723-(4-phenylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene

Product 1

HCID 22989966methyl 3-(4-phenylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylateYield 73%

Conditions

Temperature
110 °C

Procedure

To 3-(4-phenylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene (2.90 g, 8.47 mmol) dissolved in dimethyl carbonate (80 ml) was added sodium methoxide (2.29 g, 42.4 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 a mixed solvent of ethyl acetate and THF ((30 ml/15 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: 50 g, ethyl acetate/hexane=1/30). The objective fractions were concentrated under reduced pressure, diisopropyl ether was added to the residue and an insoluble material was collected by filtration. The insoluble material was washed with diisopropyl ether and was then dried under reduced pressure to obtain methyl 3-(4-phenylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylate (2.47 g, 6.17 mmol, 73%).

Workup

  1. temperatureat reflux
  2. concentrationwas concentrated under reduced pressure
  3. customto remove the organic solvent
  4. extractionthe aqueous layer was extracted with a mixed solvent of ethyl acetate and THF ((30 ml/15 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, diisopropyl ether
  8. additionwas added to the residue
  9. filtrationan insoluble material was collected by filtration
  10. washThe insoluble material was washed with diisopropyl ether
  11. customwas then dried under reduced pressure

Sources & evidence

ORD record
ord-d80ab131486149f2a152f2f4a6bc6a93
Source dataset
uspto-grants-2003_09
Patent number
US06627651B1

Reaction notes

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