Sodium hydride → 3-Dimethylamino-2-(cholest-5-en-3beta-oxybutan-4-oxy)-1-(cis,cis-9,12-octadecadienoxy)propane

HRID 638766Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 638766
[CH3:1][N:2]([CH3:40])[CH2:3][CH:4]([O:7][CH:8]([O:12][C@H:13]1[CH2:37][CH2:36][C@@:35]2([CH3:38])[C:15](=[CH:16][CH2:17][C@@H:18]3[C@@H:34]2[CH2:33][CH2:32][C@@:31]2([CH3:39])[C@H:19]3[CH2:20][CH2:21][C@@H:22]2[C@H:23]([CH3:30])[CH2:24][CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])[CH2:14]1)[CH2:9][CH2:10][CH3:11])[CH2:5][OH:6].[H-].[Na+].S(O[CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55]/[CH:56]=[CH:57]\[CH2:58]/[CH:59]=[CH:60]\[CH2:61][CH2:62][CH2:63][CH2:64][CH3:65])(=O)(=O)C>C1(C)C=CC=CC=1>[CH3:40][N:2]([CH3:1])[CH2:3][CH:4]([O:7][CH:8]([O:12][C@H:13]1[CH2:37][CH2:36][C@@:35]2([CH3:38])[C:15](=[CH:16][CH2:17][C@@H:18]3[C@@H:34]2[CH2:33][CH2:32][C@@:31]2([CH3:39])[C@H:19]3[CH2:20][CH2:21][C@@H:22]2[C@H:23]([CH3:30])[CH2:24][CH2:25][CH2:26][CH:27]([CH3:28])[CH3:29])[CH2:14]1)[CH2:9][CH2:10][CH3:11])[CH2:5][O:6][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55]/[CH:56]=[CH:57]\[CH2:58]/[CH:59]=[CH:60]\[CH2:61][CH2:62][CH2:63][CH2:64][CH3:65]

Komponenten

5

Edukt 3

HCID 24758Sodium hydrideHCID 59753235Linoleyl methanesulfonateHCID 866085843-Dimethylamino-2-(Cholest-5-en-3beta-oxybutan-4-oxy)-1-propanol

Produkt 1

HCID 866085833-Dimethylamino-2-(cholest-5-en-3beta-oxybutan-4-oxy)-1-(cis,cis-9,12-octadecadienoxy)propaneAusbeute 81 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

3-Dimethylamino-2-(Cholest-5-en-3β-oxybutan-4-oxy)-1-propanol (2.6 g, 4.6 mmol) was weighed into a 200 mL round bottomed flask and co-evaporated with anhydrous toluene 2×20 mL). A stir bar was added to the flask, which was then sealed, flushed with argon and charged with anhydrous toluene (100 mL). Sodium hydride (0.7 g, 6 equiv) was added at once and the mixture was stirred, under argon, for 20 minutes. Linoleyl mesylate (4.6 g, 2.3 equiv.) was measured in a PP syringe and added slowly to the reaction mixture. The flask was fitted with a reflux condenser and the apparatus was flushed with argon. The reaction mixture was heated in an oil bath and allowed to stir at reflux overnight. The reaction mixture was then cooled to room temperature in a water bath and ethanol was added dropwise until gas evolution ceased. The reaction mixture was diluted with ethyl acetate (300 mL) and washed with aqueous 10% sodium carbonate (2×200 mL). The aqueous phases were combined and back extracted with ethyl acetate (2×100 mL). The organic phases were combined, dried over MgSO4, filtered and concentrated. The resultant oil was purified via column chromatography (10% EtOAc/Hexanes, 3% TEA) to afford 3.0 g (81%) of a colorless oil.

Aufarbeitung

  1. additionA stir bar was added to the flask, which
  2. customwas then sealed
  3. customflushed with argon
  4. additioncharged with anhydrous toluene (100 mL)
  5. additionadded slowly to the reaction mixture
  6. customThe flask was fitted with a reflux condenser
  7. customthe apparatus was flushed with argon
  8. temperatureThe reaction mixture was heated in an oil bath
  9. stirringto stir
  10. temperatureat reflux overnight
  11. additionethanol was added dropwise until gas evolution
  12. additionThe reaction mixture was diluted with ethyl acetate (300 mL)
  13. washwashed with aqueous 10% sodium carbonate (2×200 mL)
  14. extractionback extracted with ethyl acetate (2×100 mL)
  15. dry with materialdried over MgSO4
  16. filtrationfiltered
  17. concentrationconcentrated
  18. customThe resultant oil was purified via column chromatography (10% EtOAc/Hexanes, 3% TEA)

Quellen und Nachweise

ORD-Eintrag
ord-ee85086b66b9442b97985394e0bfcb8b
Quelldatensatz
uspto-grants-2010_04
Patentnummer
US07691405B2

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