Hydrochloric Acid → 3-Hydroxy-17-methyleneestra-1,3,5(10)-triene-2-carboxaldehyde

HRID 963183

Reaktionsgleichung

Reaktionsgleichung von HRID 963183
[Mg].BrCC.[CH2:5]=[C:6]1[CH2:11][CH2:10][C@H:9]2[C@H:12]3[C@H:21]([CH2:22][CH2:23][C@:7]12[CH3:8])[C:20]1[CH:19]=[CH:18][C:17]([OH:24])=[CH:16][C:15]=1[CH2:14][CH2:13]3.CN(C)P(=O)(N(C)C)N(C)C.[CH2:36]=[O:37].Cl>C1COCC1.C1C=CC=CC=1>[OH:24][C:17]1[C:18]([CH:36]=[O:37])=[CH:19][C:20]2[C@@H:21]3[C@H:12]([C@H:9]4[C@@:7]([CH2:23][CH2:22]3)([CH3:8])[C:6](=[CH2:5])[CH2:11][CH2:10]4)[CH2:13][CH2:14][C:15]=2[CH:16]=1

Komponenten

9

Edukt 6

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 6332Ethyl BromideHCID 12679HexamethylphosphoramideHCID 5462224MagnesiumHCID 1445855217-Methylene-estra-1,3,5(10)-trien-3-ol

Produkt 1

HCID 542724493-Hydroxy-17-methyleneestra-1,3,5(10)-triene-2-carboxaldehydeAusbeute 78,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 241BenzeneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

To a suspension of magnesium (0.365 g, 15 mmol) in THF (3.0 mL) was added bromoethane (1.5 mL, 20 mmol) dissolved in THF (3.0 mL) at room temperature. 17-Methyleneestra-1,3,5(10)-trien-3-ol (19, 0.805 g, 3.0 mmol) dissolved in THF (7.5 mL) was added to the reaction mixture, and stirring continued for 30 min. The solvent was removed at reduced pressure, and to the residue were added benzene (35 mL), hexamethylphosphoric triamide (1.4 mL, 7.5 mmol) and paraformaldehyde (0.630 g). Stirring was continued for 6 h at 80° C. After the reaction mixture was cooled to room temperature, 5N HCl (15 mL) was added and the mixture 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:AcOEt (10:1→3:1, v/v) to afford 0.695 g of 23 (78% yield), m.p. 128°-130° C.

Aufarbeitung

  1. additionwas added to the reaction mixture
  2. customThe solvent was removed at reduced pressure
  3. stirringStirring
  4. waitwas continued for 6 h at 80° C
  5. extractionthe mixture extracted with EtOAc
  6. washThe combined organic layers were washed with H2O
  7. dry with materialwith saturated aqueous NaCl, and dried (Na2SO4)
  8. filtrationThe desiccant was filtered
  9. customthe solvent was evaporated at reduced pressure
  10. customThe residue was purified by column chromatography (silica gel)

Quellen und Nachweise

ORD-Eintrag
ord-eebcbbfc98aa4b43a61a7b9480b666ca
Quelldatensatz
uspto-grants-1998_06
Patentnummer
US05763432

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