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N-Methyl dicyclohexylamine → HCID 86731498, Verbindung

HRID 1773039
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1773039
FC(F)(F)S(O[C:7]1[C:8]([CH3:46])([CH3:45])[C@H:9]2[C@:22]([CH3:25])([CH2:23][CH:24]=1)[C@@H:21]1[C@:12]([CH3:44])([C@@:13]3([CH3:43])[C@H:18]([CH2:19][CH2:20]1)[C@H:17]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:16]1([NH:32][CH2:33][CH2:34][N:35]1[CH2:40][CH2:39][S:38](=[O:42])(=[O:41])[CH2:37][CH2:36]1)[CH2:15][CH2:14]3)[CH2:11][CH2:10]2)(=O)=O.[C:49]([O:53][C:54]([NH:56][C:57]1([C:62]([O:64][CH2:65][CH3:66])=[O:63])[CH2:59][CH:58]1[CH:60]=[CH2:61])=[O:55])([CH3:52])([CH3:51])[CH3:50].C1(N(C)C2CCCCC2)CCCCC1>O1CCOCC1.C(OCC)C.[Pd].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>[C:49]([O:53][C:54]([NH:56][C:57]1([C:62]([O:64][CH2:65][CH3:66])=[O:63])[CH2:59][CH:58]1/[CH:60]=[CH:61]/[C:7]1[C:8]([CH3:46])([CH3:45])[C@H:9]2[C@:22]([CH3:25])([CH2:23][CH:24]=1)[C@@H:21]1[C@:12]([CH3:44])([C@@:13]3([CH3:43])[C@H:18]([CH2:19][CH2:20]1)[C@H:17]1[C@H:26]([C:29]([CH3:31])=[CH2:30])[CH2:27][CH2:28][C@:16]1([NH:32][CH2:33][CH2:34][N:35]1[CH2:36][CH2:37][S:38](=[O:42])(=[O:41])[CH2:39][CH2:40]1)[CH2:15][CH2:14]3)[CH2:11][CH2:10]2)=[O:55])([CH3:52])([CH3:50])[CH3:51]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 3

HCID 24210N-Methyl dicyclohexylamineHCID 22091725Ethyl 1-((tert-butoxycarbonyl)amino)-2-vinylcyclopropanecarboxylateHCID 71698666(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-((2-(1,1-dioxidothiomorpholino)ethyl)amino)-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 trifluoromethanesulfonate

Produkt 1

HCID 86731498
HCID 86731498, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 2734558Bis(tri-tert-butylphosphine)palladium(0)KatalysatorHCID 3283Diethyl EtherLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

The mixture of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-((2-(1,1-dioxidothiomorpholino)ethyl)amino)-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 trifluoromethanesulfonate (50 mg, 0.070 mmol), ethyl 1-((tert-butoxycarbonyl)amino)-2-vinylcyclopropanecarboxylate (17.76 mg, 0.070 mmol) and N-cyclohexyl-N-methylcyclohexanamine (0.018 mL, 0.083 mmol) in dioxane (1 mL) was placed in a sealable pressure tube and N2 was bubbled through the solution for 10 min. Bis(tri-tertbutylphosphine) Palladium(0) (0.355 mg, 0.695 μmol) was added to the reaction mixture and the tube was sealed, and heated to 110° C. for 4 h. After cooling to rt, the crude reaction mixture was diluted with diethyl ether and filtered. The filtrate was concentrated and purified using a flash silica gel column (4 g; eluted with ethyl acetate in hexane from 0 to 45%) to give the title compound as a yellow film (13 mg, 22.7%). MS: m/e 824.55 (M+H)+, 2.625 min (method 4). 1H NMR (400 MHz, CHLOROFORM-d) δ 7.23-5.36 (m, 2H), 5.27-5.12 (m, 1H), 4.72 (br. s., 1H), 4.61 (br. s., 1H), 4.26 (m, 2H), 3.24-2.92 (m, 8H), 2.72-2.45 (m, 5H), 2.32-1.76 (m, 11H), 1.68 (br. s., 3H), 1.53-0.74 (m, 42H).

Aufarbeitung

  1. customwas placed in a sealable pressure tube
  2. customN2 was bubbled through the solution for 10 min
  3. customthe tube was sealed
  4. temperatureAfter cooling to rt
  5. customthe crude reaction mixture
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. custompurified
  9. washa flash silica gel column (4 g; eluted with ethyl acetate in hexane from 0 to 45%)

Quellen und Nachweise

ORD-Eintrag
ord-d99f292f65b640ccb0a97401ad9c2ad8
Quelldatensatz
uspto-grants-2016_02
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09249180B2

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