Sodium Hydroxide → 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(furan-2-ylmethylamino)-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)benzoic acid

HRID 85644Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 85644
[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][NH:7][C@:8]12[CH2:43][CH2:42][C@@H:41]([C:44]([CH3:46])=[CH2:45])[C@@H:9]1[C@@H:10]1[C@@:23]([CH3:26])([CH2:24][CH2:25]2)[C@@:22]2([CH3:27])[C@@H:13]([C@:14]3([CH3:40])[C@@H:19]([CH2:20][CH2:21]2)[C:18]([CH3:29])([CH3:28])[C:17]([C:30]2[CH:39]=[CH:38][C:33]([C:34]([O:36]C)=[O:35])=[CH:32][CH:31]=2)=[CH:16][CH2:15]3)[CH2:12][CH2:11]1.[OH-].[Na+]>O1CCOCC1>[O:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][NH:7][C@:8]12[CH2:43][CH2:42][C@@H:41]([C:44]([CH3:46])=[CH2:45])[C@@H:9]1[C@@H:10]1[C@@:23]([CH3:26])([CH2:24][CH2:25]2)[C@@:22]2([CH3:27])[C@@H:13]([C@:14]3([CH3:40])[C@@H:19]([CH2:20][CH2:21]2)[C:18]([CH3:29])([CH3:28])[C:17]([C:30]2[CH:39]=[CH:38][C:33]([C:34]([OH:36])=[O:35])=[CH:32][CH:31]=2)=[CH:16][CH2:15]3)[CH2:12][CH2:11]1

Komponenten

4

Edukt 2

HCID 14798Sodium HydroxideHCID 86676601methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(furan-2-ylmethylamino)-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)benzoate

Produkt 1

HCID 683581384-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(furan-2-ylmethylamino)-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)benzoic acidAusbeute 60,5 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

To a solution of methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(furan-2-ylmethylamino)-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)benzoate (31 mg, 0.050 mmol) in 1,4-dioxane (2 mL) was added 1N NaOH (0.248 mL, 0.248 mmol). The mixture was heated to 85° C. for 22 h then was cooled to rt. The crude product was purified by prep HPLC. The fractions containing the expected product were combined and were concentrated under reduced pressure to afford the title compound (19.3 mg, 0.030 mmol, 60.5% yield) as a clear film. LCMS: m/e 610.69 (M+H)+, 2.35 min (method 2). 1H NMR (400 MHz, CHLOROFORM-d) d ppm 8.00 (d, J=7.78 Hz, 2H), 7.37 (d, J=1.00 Hz, 1H), 7.23 (d, J=7.78 Hz, 2H), 6.33 (dd, J=3.14, 1.88 Hz, 1H), 6.21 (d, J=2.76 Hz, 1H), 5.53 (br. s., 1H), 5.29-5.34 (m, 1H), 4.72 (d, J=1.76 Hz, 1H), 4.60 (s, 1H), 3.67 (s, 2H), 2.64 (td, J=10.85, 5.40 Hz, 1H), 1.71 (s, 3H), 1.10-1.15 (m, 3H), 1.01 (s, 3H), 1.00 (s, 3H), 0.97-2.18 (m, 22H), 0.96 (s, 6H).

Aufarbeitung

  1. temperaturethen was cooled to rt
  2. customThe crude product was purified by prep HPLC
  3. additionThe fractions containing the expected product
  4. concentrationwere concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-610cdb74e282475a9e5b26353f8d70fe
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08846647B2

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