Trifluoroacetic acid → 4-[[(3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-[(E)-3-[[1-(4-chlorophenyl)cyclopropyl]amino]-2-methyl-3-oxo-prop-1-enyl]-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3H-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxo-butanoic acid

HRID 524471Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 524471
[CH3:1][C:2]([CH3:60])([CH2:10][C:11]([O:13][C@H:14]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C@@H:16]([CH2:17][CH2:18][C@:19]3([CH3:57])[C@@H:28]2[CH2:27][CH2:26][C@H:25]2[C@@:20]3([CH3:56])[CH2:21][CH2:22][C@@:23]3(/[CH:40]=[C:41](\[CH3:55])/[C:42]([NH:44][C:45]4([C:48]5[CH:53]=[CH:52][C:51]([Cl:54])=[CH:50][CH:49]=5)[CH2:47][CH2:46]4)=[O:43])[CH2:35][C:34](=[O:36])[C:33]([CH:37]([CH3:39])[CH3:38])=[C:24]32)[C:15]1([CH3:59])[CH3:58])=[O:12])[C:3]([O:5]C(C)(C)C)=[O:4].C(O)(C(F)(F)F)=O.CC#N.O>C(Cl)Cl>[Cl:54][C:51]1[CH:50]=[CH:49][C:48]([C:45]2([NH:44][C:42](=[O:43])/[C:41](/[CH3:55])=[CH:40]/[C@:23]34[CH2:35][C:34](=[O:36])[C:33]([CH:37]([CH3:38])[CH3:39])=[C:24]3[C@@H:25]3[C@@:20]([CH3:56])([CH2:21][CH2:22]4)[C@@:19]4([CH3:57])[C@@H:28]([C@:29]5([CH3:32])[C@@H:16]([CH2:17][CH2:18]4)[C:15]([CH3:58])([CH3:59])[C@@H:14]([O:13][C:11](=[O:12])[CH2:10][C:2]([CH3:1])([CH3:60])[C:3]([OH:5])=[O:4])[CH2:31][CH2:30]5)[CH2:27][CH2:26]3)[CH2:47][CH2:46]2)=[CH:53][CH:52]=1

Komponenten

5

Edukt 3

HCID 6422Trifluoroacetic acidHCID 18373917Acetonitrile--water (1/1)HCID 1177015021-tert-butyl 4-((3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-((E)-3-((1-(4-chlorophenyl)cyclopropyl)amino)-2-methyl-3-oxoprop-1-en-1-yl)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-9-yl) 2,2-dimethylsuccinate

Produkt 1

HCID 716113104-[[(3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-[(E)-3-[[1-(4-chlorophenyl)cyclopropyl]amino]-2-methyl-3-oxo-prop-1-enyl]-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3H-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxo-butanoic acidAusbeute 53,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

To a solution of 1-tert-butyl 4-((3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-((E)-3-((1-(4-chlorophenyl)cyclopropyl)amino)-2-methyl-3-oxoprop-1-en-1-yl)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-9-yl) 2,2-dimethylsuccinate (300 mg, 0.355 mmol) in DCM (6 mL) was added TFA (3 mL, 0.355 mmol). The reaction mixture was stirred at rt for 2 hr and evaporated in vacuo to afford crude product which was diluted with DCM (30 mL) and washed with water, saturated NaHCO3, water, saturated NH4CI and water. The organic layer was dried over Na2SO4, filtered and concentrated to obtain a residue which was dissolved into MeCN—H2O (1:2, 9 mL) and freeze-dried to give the title compound (150 mg, 0.190 mmol, 53.6%) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ=12.81-11.61 (m, 1H), 8.73-8.51 (m, 1H), 7.28 (d, J=8.3 Hz, 2H), 7.22-7.04 (m, 2H), 6.54 (s, 1H), 4.39 (dd, J=4.9, 11.2 Hz, 1H), 3.23-3.10 (m, 1H), 2.79-0.44 (m, 57H); LC/MS: m/z calculated 787.5. Found 788.3 (M+1)+.

Aufarbeitung

  1. customevaporated in vacuo
  2. customto afford crude product which
  3. washwashed with water, saturated NaHCO3, water, saturated NH4CI and water
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto obtain a residue which
  8. customfreeze-dried

Quellen und Nachweise

ORD-Eintrag
ord-f01aa902ce464db898c0d186535067e8
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09340513B2

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