Ammonium Chloride → Ethyl (20Z)-20-formamido-9alpha-hydroxy-3-methoxypregna-3,5,17(20)-trien-21-oate

HRID 1613973Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1613973
CC(C)([O-:4])C.[K+].[N+:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])#[C-:8].[OH:15][C@:16]12[CH2:33][CH2:32][C@@:30]3([CH3:31])[C@@H:26]([CH2:27][CH2:28][C:29]3=O)[C@@H:25]1[CH2:24][CH:23]=[C:22]1[C@:17]2([CH3:37])[CH2:18][CH2:19][C:20]([O:35][CH3:36])=[CH:21]1.[Cl-].[NH4+]>O1CCCC1>[CH:8]([NH:7]/[C:9](=[C:29]1/[CH2:28][CH2:27][C@@H:26]2[C@:30]/1([CH3:31])[CH2:32][CH2:33][C@@:16]1([OH:15])[C@H:25]2[CH2:24][CH:23]=[C:22]2[C@:17]1([CH3:37])[CH2:18][CH2:19][C:20]([O:35][CH3:36])=[CH:21]2)/[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[O:4]

Komponenten

6

Edukt 4

HCID 25517Ammonium ChlorideHCID 533707Ethyl isocyanoacetateHCID 108600603-Methoxy-9alpha-hydroxyandrosta-3,5-dien-17-oneHCID 23665647Potassium tert-butoxide

Produkt 1

HCID 86746637Ethyl (20Z)-20-formamido-9alpha-hydroxy-3-methoxypregna-3,5,17(20)-trien-21-oateAusbeute 22,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Potassium tert. butoxide (1.71 g) was added to dry tetrahydrofuran (60 ml) under nitrogen. The solution was cooled to 0° C. and a solution of ethyl isocyanoacetate (1.64 g) in tetrahydrofuran (10 ml) was added dropwise, while keeping the temperature below 0° C. Next, a solution of 9α-hydroxy-3-methoxyandrosta-3,5-dien-17-one (3.21 g) in tetrahydrofuran (60 ml) was added. After stirring for 5 hours at room temperature the mixture was poured into 400 ml of saturated aqueous ammonium chloride solution and extracted twice with ethyl acetate. The combined organic layers were washed three times with water, dried (MgSO4) and concentrated under reduced pressure. The crude product (3.20 g) was purified by chromatography (silica gel, toluene/acetone 4/1 containing 0.1% triethylamine) to provide 0.99 g of the title compound. NMR spectra showed the formation of the Z-isomer of the title compound as a mixture of the two rotamer forms of the 20-formamido group.

Aufarbeitung

  1. customthe temperature below 0° C
  2. extractionextracted twice with ethyl acetate
  3. washThe combined organic layers were washed three times with water
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product (3.20 g) was purified by chromatography (silica gel, toluene/acetone 4/1 containing 0.1% triethylamine)

Quellen und Nachweise

ORD-Eintrag
ord-ec1702c06b8e4e89ac07e790e4ccbb2d
Quelldatensatz
uspto-grants-1993_03
Patentnummer
US05194602

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