Equilin → 17-Methylenestra-1,3,5(10),7-tetraen-3-ol

HRID 1108466Notes

Reaction equation

HRID 1108466 reaction equation
[CH3:1]C(C)([O-])C.[K+].[CH3:7][C@@:8]12[C:24](=O)[CH2:23][CH2:22][C@H:21]1[C:20]1[C@@H:11]([C:12]3[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=3[CH2:18][CH:19]=1)[CH2:10][CH2:9]2>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CS(C)=O>[CH2:1]=[C:24]1[CH2:23][CH2:22][C@H:21]2[C:20]3[C@H:11]([CH2:10][CH2:9][C@:8]12[CH3:7])[C:12]1[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=1[CH2:18][CH:19]=3

Participants

5

Reactant 2

HCID 223368EquilinHCID 23665647Potassium tert-butoxide

Product 1

HCID 2287307017-Methylenestra-1,3,5(10),7-tetraen-3-ol

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 679Dimethyl SulfoxideSolvent2×

Procedure

Methyltriphenylphosphonium bromide (1.9967 g, 5.5892 mmol) and potassium t-butoxide (627.2 mg, 5.589 mmol) suspended in 6.1 ml of anh. DMSO under argon were 1 h in an oil bath (71-83° C., after which equilin (300.0 mg, 1.118 mmol) in 6.1 ml of anh. DMSO was added via syringe. See FIG. 161. After stirring a further 70 min., the reaction mixture was poured into 40 ml of ice water and extracted three times with 25 ml portions of ether. The combined organic extracts were washed with 25 ml of brine, dried over magnesium sulfate, and filtered through diatomaceous earth. The residue was washed with 10 ml of ether and the combined filtrates were concentrated under reduced pressure. Flash chromatography (15% ethyl acetate/hexanes on silica gel) followed by preparative TLC (20% ethyl acetate/hexanes on silica gel GF, 1000μ thickness) gave an opaque white film (162.3 mg, 0.6093 mmol, 54%).

Workup

  1. extractionextracted three times with 25 ml portions of ether
  2. washThe combined organic extracts were washed with 25 ml of brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered through diatomaceous earth
  5. washThe residue was washed with 10 ml of ether
  6. concentrationthe combined filtrates were concentrated under reduced pressure
  7. customgave an opaque white film (162.3 mg, 0.6093 mmol, 54%)

Sources & evidence

ORD record
ord-1b07590e6d84472dbd839fffcf215328
Source dataset
uspto-grants-2000_05
Patent number
US06066627

Reaction notes

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