Hydrochloric Acid → 6-methoxy-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-one

HRID 418894Notes

Reaction equation

HRID 418894 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]2[C:15](O)=O)[CH:6]=[CH:7][CH:8]=1.C(Cl)Cl.C(Cl)(=O)[C:22](Cl)=[O:23].Cl>Cl[Ti](Cl)(Cl)Cl.CN(C=O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:6](=[CH:7][CH:8]=1)[C:22](=[O:23])[CH2:15][CH:10]1[CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 65578Oxalyl chlorideHCID 666520362-(3-Methoxy-phenyl)-cyclohexane carboxylic acid

Product 1

HCID 110316906-methoxy-2,3,4,4a,10,10a-hexahydro-1H-phenanthren-9-oneYield 93%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6228DimethylformamideSolvent

Procedure

Combine 2-(3-methoxy-phenyl)-cyclohexane carboxylic acid (11.50 g, 46.3 mmol), methylene chloride (200 mL), catalytic DMF (4.0 mL) and slowly add oxalyl chloride (4.8 mL, 55.6 mmol), stir at room temperature. After 1.5 hours, at 0° C. add TiCl4 (12.7 mL, 115.78 mmol) and let reaction warm to room temperature. After 3.5 hours, quench reaction with ice water and add 5N HCl. Allow reaction mixture to stir for 30 minutes then extract with ethyl acetate and wash with sodium bicarbonate solution (aq), then Brine. Dry the organic phase with anhydrous sodium sulfate then concentrate and flash chromatograph using 0% to 20% ethyl acetate/hexanes to yield the titled compound (9.91 g, 93%) as a yellow oil. TLC Rf=0.26 in 5:1 hexanes:ethyl acetate 1H NMR (CDCl3): 8.01 (d, 1H, J=8.8 Hz), 6.83 (m, 1H), 6.72 (m, 1H), 3.86 (s, 3H), 2.89 (m, 2H), 2.45 (m, 2H), 1.60 (m, 8H).

Workup

  1. customreaction
  2. waitAfter 3.5 hours
  3. customquench
  4. customreaction with ice water
  5. customAllow reaction mixture
  6. extractionthen extract with ethyl acetate
  7. washwash with sodium bicarbonate solution (aq)
  8. dry with materialDry the organic phase with anhydrous sodium sulfate
  9. concentrationthen concentrate

Sources & evidence

ORD record
ord-f7a63b8d1cb541c1806b9e9c29d90f43
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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