Hydrochloric Acid → (3beta)-25-[[(1,1-Dimethylethyl) dimethylsilyl]oxy]-3-[[dimethyl(1,1,2-trimethylpropyl)silyl]oxy] cholesta-5,7,16-trien-23-yn-22-ol

HRID 275511

Reaktionsgleichung

Reaktionsgleichung von HRID 275511
[CH3:1][C:2]([Si:7]([O:10][C@H:11]1[CH2:29][CH2:28][C@@:27]2([CH3:30])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:26]2[CH2:25][CH2:24][C@@:23]2([CH3:31])[C@H:17]3[CH2:18][CH2:19]/[C:20]/2=[CH:21]/[CH3:22])[CH2:12]1)([CH3:9])[CH3:8])([CH3:6])[CH:3]([CH3:5])[CH3:4].[CH3:32][C:33]([Si:36]([CH3:46])([CH3:45])[O:37][C:38]([CH3:44])([CH3:43])[C:39]#[C:40][CH:41]=[O:42])([CH3:35])[CH3:34].[Cl-].C[Al+]C.OP([O-])([O-])=O.[Na+].[Na+].Cl>CCCCCC>[CH3:35][C:33]([Si:36]([CH3:46])([CH3:45])[O:37][C:38]([C:39]#[C:40][CH:41]([OH:42])[C@H:21]([C:20]1[C@:23]2([CH3:31])[C@H:17]([C:16]3[C@H:26]([CH2:25][CH2:24]2)[C@:27]2([CH3:30])[C:13]([CH2:12][C@@H:11]([O:10][Si:7]([CH3:8])([CH3:9])[C:2]([CH3:1])([CH3:6])[CH:3]([CH3:4])[CH3:5])[CH2:29][CH2:28]2)=[CH:14][CH:15]=3)[CH2:18][CH:19]=1)[CH3:22])([CH3:44])[CH3:43])([CH3:32])[CH3:34]

Komponenten

7

Edukt 5

HCID 313Hydrochloric AcidHCID 24203Sodium Phosphate, DibasicHCID 10433395(3beta,17Z)-(1,1,2-trimethylpropyl)(pregna-5,7,17(20)-trien-3-yloxy)dimethylsilaneHCID 108896204-((Tert-butyldimethylsilyl)oxy)-4-methylpent-2-ynalHCID 16686359Dimethylalumanylium chloride

Produkt 1

HCID 10258894(3beta)-25-[[(1,1-Dimethylethyl) dimethylsilyl]oxy]-3-[[dimethyl(1,1,2-trimethylpropyl)silyl]oxy] cholesta-5,7,16-trien-23-yn-22-ol

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8058HexaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-40 °C

Versuchsvorschrift

A mixture of 57.65 g (131 mmol) (3β,17Z)-(1,1,2-trimethylpropyl)(pregna-5,7,17(20)-trien-3-yloxy)dimethylsilane, 34.11 g (151 mmol) 4-[[(1,1-dimethylethyl)dimethylsilyl]oxy-4-methyl-2-pentynal, and 800 mL hexane was cooled to about -40°0 C. Then, 185 mL (185 mmol) 1M dimethylaluminum chloride in hexane was added dropwise within 30 min. After the dark brown solution was stirred at -40° C. for 30 min, 400 mL of 5% aqueous sodium phosphate dibasic (w/v) was added dropwise, and the mixture was allowed to warm to 5° C. Then, 300 mL of 3N HCl was added dropwise at a temperature of 0°-5° C. followed by 40 g of Celite. After 15 min, the solid was filtered and washed with 400 mL of hexane. The aqueous layer was extracted twice with hexane. The combined hexane solutions were washed successively with water, 10% aqueous NaHCO3, and brine. The hexane layer was dried and concentrated to give 90 g (overweight) of crude (3β)-25-[[(1,1-dimethylethyl) dimethylsilyl]oxy]-3-[[dimethyl(1,1,2-trimethylpropyl)silyl]oxy] cholesta-5,7,16-trien-23-yn-22-ol (5:1 mixture of epimers at C-22) as an orange oil. This crude material was used for the next step.

Aufarbeitung

  1. temperaturewas cooled to about -40°0 C
  2. temperatureto warm to 5° C
  3. waitAfter 15 min
  4. filtrationthe solid was filtered
  5. washwashed with 400 mL of hexane
  6. extractionThe aqueous layer was extracted twice with hexane
  7. washThe combined hexane solutions were washed successively with water, 10% aqueous NaHCO3, and brine
  8. dry with materialThe hexane layer was dried
  9. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-021d748f1f3c4ad2a8371cda6c1d2bca
Quelldatensatz
uspto-grants-1995_02
Patentnummer
US05393900

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