Dimethylformamide → 9-(4-Hydroxy-phenyl)-10-methoxymethyl-4b,5,6,7,8,8a,9,10-octahydro-phenanthren-3-ol

HRID 418970Notes

Reaction equation

HRID 418970 reaction equation
C[O:2][C:3]1[CH:4]=[C:5]2[C:14](=[CH:15][CH:16]=1)[CH:13]([CH2:17][O:18][CH3:19])[CH:12]([C:20]1[CH:25]=[CH:24][C:23]([O:26]C)=[CH:22][CH:21]=1)[CH:11]1[CH:6]2[CH2:7][CH2:8][CH2:9][CH2:10]1.C([S-])C.[Na+].CN(C=O)C>C(OCC)(=O)C>[OH:26][C:23]1[CH:24]=[CH:25][C:20]([CH:12]2[CH:13]([CH2:17][O:18][CH3:19])[C:14]3[CH:15]=[CH:16][C:3]([OH:2])=[CH:4][C:5]=3[CH:6]3[CH:11]2[CH2:10][CH2:9][CH2:8][CH2:7]3)=[CH:21][CH:22]=1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 4459711Sodium ethanethiolateHCID 666519026-Methoxy-9-methoxymethyl-10-(4-methoxy-phenyl)-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene

Product 1

HCID 666519829-(4-Hydroxy-phenyl)-10-methoxymethyl-4b,5,6,7,8,8a,9,10-octahydro-phenanthren-3-olYield 33%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Combine 6-methoxy-9-methoxymethyl-10-(4-methoxy-phenyl)-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene (0.050 g, 0.14 mmol), sodium ethanethiolate (0.037 g, 0.44 mmol), and DMF (4 mL), and reflux under nitrogen atmosphere. After 18 hours, cool the reaction to room temperature and add ethyl acetate, wash with sat ammonium chloride solution (aq), then brine several times. Concentrate, and purify using reverse phase chromatography (5% to 95% 0.001% TFA buffer in acetonitrile/water) to yield the titled compound (0.015 g, 33%) as a white solid. TLC Rf=0.27 in 3:1 hexanes:ethyl acetate. 1H NMR (d-methanol): 7.42 (d, 1H, J=8.4 Hz), 7.13 (d, 2H, J=8.4 Hz), 6.84 (s, 1H), 6.79 (d, 2H, J=8.4 Hz), 6.65 (dd, 1H, J=7.9, 1.8 Hz), 3.70 (d, 1H, J=7.0 Hz), 3.35 (m, 3H), 3.17 (s, 3H), 3.07 (m, 1H), 2.48 (d, 1H, J=14.1 Hz), 1.87 (m, 1H), 1.64 (m, 2H), 1.41 (m, 2H), 1.16 (m, 3H).

Workup

  1. temperaturecool
  2. customthe reaction to room temperature
  3. washwash with sat ammonium chloride solution (aq)
  4. concentrationConcentrate
  5. custompurify

Sources & evidence

ORD record
ord-ba9f58d2808e4da498f3448912bbe0b5
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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