Acetic Acid → (1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-1-isopropyl-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid

HRID 2405478

Reaktionsgleichung

Reaktionsgleichung von HRID 2405478
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:12]([CH3:49])([CH3:48])[C@H:13]3[C@:26]([CH3:29])([CH2:27][CH:28]=2)[C@@H:25]2[C@:16]([CH3:47])([C@@:17]4([CH3:46])[C@H:22]([CH2:23][CH2:24]2)[C@H:21]2[C@H:30]([C:33]([CH3:35])=[CH2:34])[CH2:31][CH2:32][C@:20]2([C:36]([O:38]CC2C=CC=CC=2)=[O:37])[CH2:19][CH2:18]4)[CH2:15][CH2:14]3)=[CH:7][CH:6]=1)=[O:4].C(O)(=O)C>C(O)C.O1CCOCC1.[Pd]>[CH:33]([C@H:30]1[C@@H:21]2[C@@H:22]3[C@@:17]([CH3:46])([CH2:18][CH2:19][C@@:20]2([C:36]([OH:38])=[O:37])[CH2:32][CH2:31]1)[C@@:16]1([CH3:47])[C@@H:25]([C@:26]2([CH3:29])[C@@H:13]([CH2:14][CH2:15]1)[C:12]([CH3:49])([CH3:48])[C@@H:11]([C:8]1[CH:7]=[CH:6][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:10][CH:9]=1)[CH2:28][CH2:27]2)[CH2:24][CH2:23]3)([CH3:35])[CH3:34]

Komponenten

6

Edukt 2

HCID 176Acetic AcidHCID 67776728(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR 13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate

Produkt 1

HCID 67775516(1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-1-isopropyl-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acidAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23938PalladiumKatalysatorHCID 702EthanolLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate (0.2 g, 0.302 mmol) in ethanol (5 mL), 1,4-dioxane (7 mL), and acetic acid (0.5 mL, 8.73 mmol) was added Pd/C (10% by wt.) (0.1 g, 0.094 mmol). The mixture was flushed with N2 and was put on the Parr shaker under 30 psi H2. After 2 h, the reaction was checked by 1H NMR. The benzyl group had been removed, but the alkene still remained. The mixture was again flushed with N2. An additional 50 mg of 10% Pd/C was added and the mixture was pressurized to 40 psi H2. After stirring the mixture overnight, it reaction was removed from the Parr shaker and the palladium catalyst was removed by filtration. The filtrate was concentrated under reduced pressure to give the expected product, (1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-1-isopropyl-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (0.174 g, 100% yield), as a white solid. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 7.91 (d, J=8.24 Hz, 2H), 7.22 (d, J=8.55 Hz, 2H), 3.89 (s, 3H), 2.39 (dd, J=13.12, 3.05 Hz, 1H), 2.19-2.29 (m, 3H), 2.01-2.13 (m, 1H), 0.99 (s, 3H), 0.96 (s, 3H), 0.95 (s, 3H), 0.86 (d, J=6.71 Hz, 3H), 0.79-1.92 (m, 22H), 0.76 (d, J=6.71 Hz, 3H), 0.75 (s, 3H), 0.68 (s, 3H).

Aufarbeitung

  1. customThe mixture was flushed with N2
  2. customThe benzyl group had been removed
  3. customThe mixture was again flushed with N2
  4. additionAn additional 50 mg of 10% Pd/C was added
  5. customthe mixture overnight, it reaction
  6. customwas removed from the Parr shaker
  7. customthe palladium catalyst was removed by filtration
  8. concentrationThe filtrate was concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-cd4f46976fef4658b02d11706bd6a979
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08802661B2

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