Water → HCID 69788035, compound

HRID 1815775Notes

Reaction equation

HRID 1815775 reaction equation
[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C:12](=O)[CH2:11][CH2:10]4)[CH2:7][CH2:6][C:5]=2[CH:4]=1.O.[C:23]1(C)C=CC=CC=1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CS(C)=O>[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C:12](=[CH2:23])[CH2:11][CH2:10]4)[CH2:7][CH2:6][C:5]=2[CH:4]=1

Participants

6

Reactant 3

HCID 962WaterHCID 1140Toluene2×HCID 7213843HCID 7213843, compound

Product 1

HCID 69788035HCID 69788035, compound

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
65 °C

Procedure

—Lithium amide (6.6 g) was added to a suspension of methyltriphenylphosphonium bromide (113 g) in dry toluene (300 ml) and dry dimethyl sulfoxide (24 ml). The reaction mixture was heated to 65° C. for 30 min. After cooling to 35-40° C., a solution of (14β)-3-methoxyestra-1,3,5(10)-trien-17-one [Johnson, W. S. et al, J. Am. Chem. Soc. 79, 2005 (1957); 30 g] in dry toluene (225 ml) was added and the mixture was heated at 60° C. for 22 h. Then it was cooled and poured into water. The product was extracted into ethyl acetate; the combined organic phases were dried over sodium sulfate and concentrated under reduced pressure. In order to achieve complete conversion of starting material, the procedure was repeated. The triphenylphosphine oxide was removed by addition of diethyl ether and filtration. Column chromatography of the crude product afforded (14β)-3-methoxy-17-methyleneestra-1,3,5(10)-triene (26 g).

Workup

  1. temperatureAfter cooling to 35-40° C.
  2. temperaturethe mixture was heated at 60° C. for 22 h
  3. temperatureThen it was cooled
  4. extractionThe product was extracted into ethyl acetate
  5. dry with materialthe combined organic phases were dried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe triphenylphosphine oxide was removed by addition of diethyl ether and filtration

Sources & evidence

ORD record
ord-5a4de9626a214db79881252870c03f6a
Source dataset
uspto-grants-2005_04
Patent number
US06881728B1

Reaction notes

Loading…