Estrone → 17-Methylene-estra-1,3,5(10)-trien-3-ol

HRID 343306

Reaction equation

HRID 343306 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@H:20]1[C@@H:11]([C:12]3[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=3[CH2:18][CH2:19]1)[CH2:10][CH2:9]2>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH2:1]=[C:24]1[CH2:23][CH2:22][C@H:9]2[C@H:10]3[C@H:11]([CH2:20][CH2:21][C@:8]12[CH3:7])[C:12]1[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=1[CH2:18][CH2:19]3

Participants

5

Reactant 2

HCID 5870EstroneHCID 23665647Potassium tert-butoxide

Product 1

HCID 1445855217-Methylene-estra-1,3,5(10)-trien-3-olYield 84%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of methyl triphenylphosphonium bromide (8.93 g, 25.0 mmol) in THF (120 mL) was added potassium tert-butoxide (2.69 g, 24 mmol) and stirred for 30 min at room temperature. The reaction mixture was added estrone (18, 2.70 g, 10 mmol), stirred for 19 h at room temperature. The reaction mixture was quenched with saturated aqueous NH4Cl at 0° C. and extracted with EtOAc. The combined organic layers were washed with H2O, then with saturated aqueous NaCl, and dried (Na2SO4). The desiccant was filtered and the solvent was evaporated at reduced pressure. The residue was purified by column chromatography (silica gel) using n-hexane:EtOAc (5:1→3:1, v/v) to afford 2.24 g of 19 (84% yield), m.p. 135°-136° C.

Workup

  1. stirringstirred for 19 h at room temperature
  2. customThe reaction mixture was quenched with saturated aqueous NH4Cl at 0° C.
  3. extractionextracted with EtOAc
  4. washThe combined organic layers were washed with H2O
  5. dry with materialwith saturated aqueous NaCl, and dried (Na2SO4)
  6. filtrationThe desiccant was filtered
  7. customthe solvent was evaporated at reduced pressure
  8. customThe residue was purified by column chromatography (silica gel)

Sources & evidence

ORD record
ord-3d84aa02f6df439dad14156f8d5d930f
Source dataset
uspto-grants-1999_01
Patent number
US05861388

Linked notes

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