Ammonium Chloride → tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aminomethyl)-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)benzoate

HRID 405100Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 405100
O[N:2]=[CH:3][C@:4]12[CH2:42][CH2:41][C@@H:40]([C:43]([CH3:45])=[CH2:44])[C@@H:5]1[C@@H:6]1[C@@:19]([CH3:22])([CH2:20][CH2:21]2)[C@@:18]2([CH3:23])[C@@H:9]([C@:10]3([CH3:39])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]2[CH:38]=[CH:37][C:29]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])=[CH:28][CH:27]=2)=[CH:12][CH2:11]3)[CH2:8][CH2:7]1.[NH4+].[Cl-].[Na]>[Cl-].[Ti+3].[Cl-].[Cl-].CCO>[NH2:2][CH2:3][C@:4]12[CH2:42][CH2:41][C@@H:40]([C:43]([CH3:45])=[CH2:44])[C@@H:5]1[C@@H:6]1[C@@:19]([CH3:22])([CH2:20][CH2:21]2)[C@@:18]2([CH3:23])[C@@H:9]([C@:10]3([CH3:39])[C@@H:15]([CH2:16][CH2:17]2)[C:14]([CH3:25])([CH3:24])[C:13]([C:26]2[CH:38]=[CH:37][C:29]([C:30]([O:32][C:33]([CH3:34])([CH3:35])[CH3:36])=[O:31])=[CH:28][CH:27]=2)=[CH:12][CH2:11]3)[CH2:8][CH2:7]1

Komponenten

6

Edukt 3

HCID 25517Ammonium ChlorideHCID 5360545SodiumHCID 86676421tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((hydroxyimino)methyl)-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)benzoate

Produkt 1

HCID 86676419tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(aminomethyl)-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)benzoate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 10313229titanium(III) trichlorideKatalysatorHCID 702EthanolLösungsmittel

Versuchsvorschrift

To the crude product from above containing tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((hydroxyimino)methyl)-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)benzoate (100 mg, 0.163 mmol) in a 100 mL pear shape flask was added EtOH (12 mL) to form a clear solution. To this was added excess of NH4Cl (400 mg, 5.19 mmol) and sodium cyanoborohydre (300 mg, 4.77 mmol). The mixture was stirred in an ice bath until cold. To this suspension was added titanium(III) chloride (4 mL, 0.163 mmol) 20% solution. The resulting mixture was blanketed with nitrogen. The ice bath was removed and the stirring was continued at rt for an hour. LCMS show the reaction was complete. At this point, the mixture was dark greenish-blue-purple. A solution of sodium hydroxide (3 mL, 10N in 25 mL water) was added into the reaction mixture, along with methylene chloride (30 mL).

Aufarbeitung

  1. customto form a clear solution
  2. customThe ice bath was removed
  3. waitthe stirring was continued at rt for an hour
  4. additionA solution of sodium hydroxide (3 mL, 10N in 25 mL water) was added into the reaction mixture, along with methylene chloride (30 mL)

Quellen und Nachweise

ORD-Eintrag
ord-d32393327a9a49439416ade6c55c209b
Quelldatensatz
uspto-grants-2014_06
Patentnummer
US08748415B2

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