Ethanol → ethyl 10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene-2-carboxylate

HRID 452177Notes

Reaction equation

HRID 452177 reaction equation
C(C1N(C[C:15]2[CH:32]=[CH:31][C:18]3/[C:19](=[CH:28]/[C:29]#N)/[C:20]4C=CC=C[C:21]=4[CH2:22][CH2:23][C:17]=3[CH:16]=2)C2=NC(C)=CC(C)=C2N=1)C.[CH:33]([O:40]CC)([O:37][CH2:38][CH3:39])OCC.S(=O)(=O)(O)O.[CH2:48]([OH:50])[CH3:49]>C(OCC)(=O)C>[O:50]=[C:48]1[C:16]2[CH:15]=[CH:32][C:31]([C:33]([O:37][CH2:38][CH3:39])=[O:40])=[CH:18][C:17]=2[CH2:23][CH2:22][C:21]2[CH:20]=[CH:19][CH:28]=[CH:29][C:49]1=2

Participants

6

Reactant 4

HCID 702EthanolHCID 1118Sulfuric AcidHCID 31214Ethyl orthoformateHCID 22858094(E)-[2-(2-ethyl-5,7-dimethyl-3H-imidazo[4,5-b]pyridin-3-yl)methyl-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene]acetonitrile

Product 1

HCID 67211051ethyl 10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene-2-carboxylateYield 94%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

[step 1] 5-Oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-2-carboxylic acid (JP-B-2526005, 19.9 g, 79 mmol) and triethyl orthoformate (17.0 mL, 102 mmol) were dissolved in ethanol (130 mL), concentrated sulfuric acid (1.68 mL, 32 mmol) was added, and the mixture was stirred under reflux for 12 hr. The mixture was diluted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=90/10) to give ethyl 5-oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-2-carboxylate (20.8 g, 94%).

Workup

  1. temperatureunder reflux for 12 hr
  2. washthe organic layer was washed with saturated aqueous sodium hydrogen carbonate solution
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=90/10)

Sources & evidence

ORD record
ord-eeb5a6c72c7d478aa7cceb67c2063044
Source dataset
uspto-grants-2013_07
Patent number
US08486980B2

Reaction notes

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