Diisopropylethylamine → ethyl 4-((1R,3 aS,5aR,5bR,7aR,11aS,11bR,13 aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(4-(methylsulfonyl)piperazin-1-yl)ethyl)amino)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate

HRID 1400987Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1400987
[N:1]1([C@:4]23[CH2:40][CH2:39][C@@H:38]([C:41]([CH3:43])=[CH2:42])[C@@H:5]2[C@@H:6]2[C@@:19]([CH3:22])([CH2:20][CH2:21]3)[C@@:18]3([CH3:23])[C@@H:9]([C@:10]4([CH3:37])[C@@H:15]([CH2:16][CH2:17]3)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]3[CH2:31][CH2:30][CH:29]([C:32]([O:34][CH2:35][CH3:36])=[O:33])[CH2:28][CH:27]=3)=[CH:12][CH2:11]4)[CH2:8][CH2:7]2)[CH2:3][CH2:2]1.[CH3:44][S:45]([N:48]1[CH2:53][CH2:52][NH:51][CH2:50][CH2:49]1)(=[O:47])=[O:46].CCN(C(C)C)C(C)C>O1CCOCC1>[CH3:22][C@:19]12[C@@:18]3([CH3:23])[C@@H:9]([C@:10]4([CH3:37])[C@@H:15]([CH2:16][CH2:17]3)[C:14]([CH3:24])([CH3:25])[C:13]([C:26]3[CH2:31][CH2:30][CH:29]([C:32]([O:34][CH2:35][CH3:36])=[O:33])[CH2:28][CH:27]=3)=[CH:12][CH2:11]4)[CH2:8][CH2:7][C@@H:6]1[C@H:5]1[C@H:38]([C:41]([CH3:43])=[CH2:42])[CH2:39][CH2:40][C@:4]1([NH:1][CH2:2][CH2:3][N:51]1[CH2:52][CH2:53][N:48]([S:45]([CH3:44])(=[O:47])=[O:46])[CH2:49][CH2:50]1)[CH2:21][CH2:20]2

Komponenten

5

Edukt 3

HCID 81531DiisopropylethylamineHCID 7091611-(Methylsulfonyl)piperazineHCID 86692341ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate

Produkt 1

HCID 86692342ethyl 4-((1R,3 aS,5aR,5bR,7aR,11aS,11bR,13 aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(4-(methylsulfonyl)piperazin-1-yl)ethyl)amino)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a flask containing the crude ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aziridin-1-yl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate (0.094 g, 0.16 mmol), was added 1-Methanesulfonyl-piperazine (0.131 g, 0.800 mmol). The mixture was diluted with 1,4-dioxane (2 mL) and Hunig's base (0.168 mL, 0.960 mmol) was added. The mixture was attached to a reflux condensor and was heated to 100° C. for 24 h then was cooled to rt, concentrated under reduced pressure, and adsorbed to silica gel. The mixture was purified by flash chromatography using a 12 g silica gel column and a 20-80% ethyl acetate in hexanes gradient. The fractions containing the product were combined and concentrated under reduced pressure to give ethyl 4-((1R,3 aS,5aR,5bR,7aR,11aS,11bR,13 aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-(4-(methylsulfonyl)piperazin-1-yl)ethyl)amino)-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate as an off-white solid. LCMS: m/e 752.8 (M+H)+, 2.22 min (method 1).

Aufarbeitung

  1. additionwas added
  2. temperaturethen was cooled to rt
  3. concentrationconcentrated under reduced pressure
  4. customThe mixture was purified by flash chromatography
  5. additionThe fractions containing the product
  6. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-be2c33e028894a4a8077cd6bf75c04a0
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08906889B2

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