Triethylamine → 20,20-Ethylenedioxy-2alpha-methyl-5alpha-pregnane-3,11-dione

HRID 1606487Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1606487
P(OC)(OC)OC.C(N(CC)CC)C.[CH2:15]1[CH2:43][O:42][C:17]([C@@H:19]2[C@:36]3([CH3:37])[C@H:22]([C@H:23]4[C@H:33]([C:34](=[O:38])[CH2:35]3)[C@:31]3([CH3:32])[C@H:26]([CH2:27][C:28](=[O:41])[C:29](=[CH:39]O)[CH2:30]3)[CH2:25][CH2:24]4)[CH2:21][CH2:20]2)([CH3:18])[O:16]1>C(O)(C)C.O.Cl.Cl.Cl[Ir](Cl)(Cl)Cl>[CH2:43]1[CH2:15][O:16][C:17]([C@@H:19]2[C@:36]3([CH3:37])[C@H:22]([C@H:23]4[C@H:33]([C:34](=[O:38])[CH2:35]3)[C@:31]3([CH3:32])[C@H:26]([CH2:27][C:28](=[O:41])[C@H:29]([CH3:39])[CH2:30]3)[CH2:25][CH2:24]4)[CH2:21][CH2:20]2)([CH3:18])[O:42]1

Komponenten

6

Edukt 3

HCID 8471TriethylamineHCID 8472Trimethyl phosphiteHCID 8673333120,20-Ethylenedioxy 2-hydroxymethylene-5alpha-pregnane-3,11-dione

Produkt 1

HCID 8673333020,20-Ethylenedioxy-2alpha-methyl-5alpha-pregnane-3,11-dioneAusbeute 6,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 16211483Tetrachloroiridium--hydrogen chloride--water (1/2/1)KatalysatorHCID 3776IsopropanolLösungsmittel

Versuchsvorschrift

A solution of chloroiridic acid (30 mg.) and trimethyl phosphite (4.5 ml.) in aqueous 90% isopropanol (60 ml.) was heated under reflux for 17 hr. The solution was then neutralised with triethylamine and 20,20-ethylenedioxy 2-hydroxymethylene-5α-pregnane-3,11-dione (2 g.) was added. The mixture was heated under reflux for 40 hr. then cooled and partitioned between water and methylene chloride. The organic layer was dried (MgSO4) and evaporated in vacuo. The residue (1.94 g.) was subjected to preparative t.l.c. giving two fractions. The less polar fraction (0.18 g.) was crystallised from methanol to give 20,20-ethylenedioxy-2α-methyl-5α-pregnane-3,11-dione (0.13 g.), m.p. 179°-180°, [α]D + 77.5°.

Aufarbeitung

  1. temperatureunder reflux for 17 hr
  2. additionwas added
  3. temperatureThe mixture was heated
  4. temperatureunder reflux for 40 hr
  5. temperaturethen cooled
  6. custompartitioned between water and methylene chloride
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customevaporated in vacuo
  9. customgiving two fractions
  10. customThe less polar fraction (0.18 g.) was crystallised from methanol

Quellen und Nachweise

ORD-Eintrag
ord-697ca9dfd62f4d70aedfd9132700c478
Quelldatensatz
uspto-grants-1976_04
Patentnummer
US03953429

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