Hydrochloric Acid → 2-Formyl-17beta-estradiol

HRID 343302

Reaktionsgleichung

Reaktionsgleichung von HRID 343302
[CH3:1][C@@:2]12[C@@H:18]([OH:19])[CH2:17][CH2:16][C@H:15]1[C@H:14]1[C@@H:5]([C:6]3[CH:7]=[CH:8][C:9]([OH:20])=[CH:10][C:11]=3[CH2:12][CH2:13]1)[CH2:4][CH2:3]2.C1N2CN3CN(C2)CN1C3.FC(F)(F)[C:33](O)=[O:34].[C:38](=O)([O-])[O-:39].[K+].[K+].Cl>CO.CCOC(C)=O.O>[OH:20][C:9]1[C:8]([CH:33]=[O:34])=[CH:7][C:6]2[C@@H:5]3[C@H:14]([C@H:15]4[C@@:2]([CH2:3][CH2:4]3)([CH3:1])[C@@H:18]([OH:19])[CH2:17][CH2:16]4)[CH2:13][CH2:12][C:11]=2[CH:10]=1.[OH:20][C:9]1[CH:8]=[CH:7][C:6]2[C@@H:5]3[C@H:14]([C@H:15]4[C@@:2]([CH2:3][CH2:4]3)([CH3:1])[C@@H:18]([OH:19])[CH2:17][CH2:16]4)[CH2:13][CH2:12][C:11]=2[C:10]=1[CH:38]=[O:39]

Komponenten

10

Edukt 5

HCID 313Hydrochloric AcidHCID 4101HexamethylenetetramineHCID 5757EstradiolHCID 6422Trifluoroacetic acidHCID 11430Potassium Carbonate

Produkt 2

HCID 99949802-Formyl-17beta-estradiolAusbeute 13 %HCID 117223424-Formyl-17beta-estradiolAusbeute 4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a mixture of estradiol (1, 13.6 g, 50 mmol) and hexamethylenetetramine (21.0 g, 150 mmol) was added trifluoroacetic acid (100 mL) at room temperature. The reaction mixture was stirred for 6 h at 100° C., poured into H2O (300 mL), and extracted with Et2O. The combined organic layers were washed with H2O, then with saturated aqueous NaCl, and dried (MgSO4). The desiccant was filtered and the solvent was evaporated at reduced pressure. The residue was dissolved in THF (50 mL) and MeOH (50 mL), potassium carbonate (6.9 g, 50 mmol) was added, and the mixture stirred for 1 h at room temperature. The reaction mixture was then diluted with EtOAc, acidified with 1N HCl, and extracted with EtOAc. The combined organic layers were washed with H2O, then with saturated aqueous NaCl, and dried (MgSO4). The desiccant was filtered and the solvent was evaporated at reduced pressure. The residue was purified by column chromatography (silica gel) using n-hexane:THF (5:1→3:1, v/v) to afford 1.91 g of 2a (13% yield), m.p. 219°-221° C., and 0.552 g of 2b (4% yield), m.p. 146°-147° C.

Aufarbeitung

  1. extractionextracted with Et2O
  2. washThe combined organic layers were washed with H2O
  3. dry with materialwith saturated aqueous NaCl, and dried (MgSO4)
  4. filtrationThe desiccant was filtered
  5. customthe solvent was evaporated at reduced pressure
  6. dissolutionThe residue was dissolved in THF (50 mL)
  7. stirringthe mixture stirred for 1 h at room temperature
  8. extractionextracted with EtOAc
  9. washThe combined organic layers were washed with H2O
  10. dry with materialwith saturated aqueous NaCl, and dried (MgSO4)
  11. filtrationThe desiccant was filtered
  12. customthe solvent was evaporated at reduced pressure
  13. customThe residue was purified by column chromatography (silica gel)

Quellen und Nachweise

ORD-Eintrag
ord-64e0a4d0429e46eca901b4385d431ffc
Quelldatensatz
uspto-grants-1999_01
Patentnummer
US05861388

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