Hydrochloric Acid → Ethyl (+/-)-10,11 dihydro-3-methoxy-5H-dibenzo[a,d]cycloheptene-10-acetate

HRID 1369210Notes

Reaction equation

HRID 1369210 reaction equation
O[C:2]1([CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH2:6][C:5]2[CH:13]=[C:14]([O:17][CH3:18])[CH:15]=[CH:16][C:4]=2[CH2:3]1.Cl>C(O)(=O)C.[Pd]>[CH3:18][O:17][C:14]1[CH:15]=[CH:16][C:4]2[CH2:3][CH:2]([CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:8]3[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=3[CH2:6][C:5]=2[CH:13]=1

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 18340682Ethyl (+/-)-10,11-dihydro-10-hydroxy-3-methoxy-5H-dibenzo[a,d]cycloheptene-10-acetate

Product 1

HCID 15462070Ethyl (+/-)-10,11 dihydro-3-methoxy-5H-dibenzo[a,d]cycloheptene-10-acetateYield 88.4%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
35 °C

Procedure

Ethyl (±)-10,11-dihydro-10-hydroxy-3-methoxy-5H-dibenzo[a,d]cycloheptene-10-acetate (101 g, 0.31 mole) was dissolved in glacial acetic acid (1.8 L) and 12 N HCl (28.5 mL, 0.34 mole) was added. The mixture was placed in a 2.5 L pressure bottle containing 5% Pd/C (20 g, 0.0094 mole), and the resulting mixture was shaken at 35° C. under hydrogen on a Parr hydrogenation apparatus equipped with a jacket heater. After 18 hr, the reaction was cooled to ambient temperature, and the catalyst was removed by filtration. The filtrate was concentrated to give a light yellow oil (85.1 g). This was chromatographed on silica gel (2 kg, step-gradient with 5% to 10% EtOAc/hexanes) to afford the title compound (69.1 g, 72%) as an oil: 1H NMR (250 MHz, CDCl3) δ7.05-7.22 (m, 4 H), 7.01 (d, J=8.2 Hz, 1 H), 6.76 (d, J=2.7 Hz, 1 H), 6.67 (dd, J=8.2, 2.7 Hz, 1 H), 4.30 (d, J=15.0 Hz, 1 H), 4.11-4.25 (m, 2 H), 3.85 (d, J=15.0 Hz, 1 H), 3.70-3.90 (m, 1 H), 3.77 (s, 3 H), 3.31 (dd, J=15.0, 4.1 Hz, 1 H), 2.93 (dd, J=15.0, 9.2 Hz, 1 H), 2.64 (dd, J=15.6, 5.0 Hz, 1 H), 2.52 (dd, J=15.6, 9.3 Hz, 1 H), 1.27 (t, J=7.1 Hz, 3 H).

Workup

  1. customequipped with a jacket heater
  2. temperaturethe reaction was cooled to ambient temperature
  3. customthe catalyst was removed by filtration
  4. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-191b4e8c5ddf4a299618fcf17d5af10b
Source dataset
uspto-grants-2003_06
Patent number
US06576643B2

Reaction notes

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