Nitrobenzene → 3beta,17beta-Di(trifluoroacetoxy)-9alpha-fluoro-5alpha-androstane

HRID 894502Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 894502
[F:1][C:2]([F:33])([F:32])[C:3]([O:5][C@H:6]1[CH2:23][CH2:22][C@@:21]2([CH3:24])[C@@H:8]([CH2:9][CH2:10][C@@H:11]3[C@@H:20]2[CH2:19][CH2:18][C@@:16]2([CH3:17])[C@H:12]3[CH2:13][CH2:14][C@@H:15]2[O:25][C:26](=[O:31])[C:27]([F:30])([F:29])[F:28])[CH2:7]1)=[O:4].[N+](C1C=CC=CC=1)([O-])=O.[F:43]C(F)(F)C([O-])=O.[Na+].FOC(F)(F)F>FC(Cl)(Cl)Cl>[F:1][C:2]([F:32])([F:33])[C:3]([O:5][C@H:6]1[CH2:23][CH2:22][C@@:21]2([CH3:24])[C@@H:8]([CH2:9][CH2:10][C@@H:11]3[C@:20]2([F:43])[CH2:19][CH2:18][C@@:16]2([CH3:17])[C@H:12]3[CH2:13][CH2:14][C@@H:15]2[O:25][C:26](=[O:31])[C:27]([F:29])([F:30])[F:28])[CH2:7]1)=[O:4]

Komponenten

6

Edukt 4

HCID 7416NitrobenzeneHCID 78989Hypofluorous acid, trifluoromethyl esterHCID 517019Sodium TrifluoroacetateHCID 867349623beta, 17beta-Di(trifluoroacetoxy)-5alpha-androstane

Produkt 1

HCID 867349613beta,17beta-Di(trifluoroacetoxy)-9alpha-fluoro-5alpha-androstaneAusbeute 39,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6389TrichlorofluoromethaneLösungsmittel

Versuchsvorschrift

A well-stirred solution of 3β, 17β-di(trifluoroacetoxy)-5α-androstane (2.5 g, 5.15 mmole, prepared by treatment of 5α-androstane-3β,17β-diol with trifluoroacetic anhydride in pyridine), nitrobenzene (800 mg, 6.5 mmole) and sodium trifluoroacetate (10 g, 73.5 mmole) in fluorotrichloromethane (45 ml) was treated with trifluoromethyl hypofluorite (8.5 mmole) at -20° for 2.5 hours, air being admitted to the reaction vessel during this time. Thereafter the solution was purged with nitrogen and the solvent was removed in vacuo. The residue was dissolved in chloroform and the resulting solution was washed with aqueous sodium bicarbonate and water and was then dried, whereafter the product was chromatographed on silica gel (125 g). Elution with chloroform:hexane (3:7) gave unreacted starting material (308 mg), while subsequent elution with chloroform:hexane (7:13) gave 3β,17β-di(trifluoroacetoxy)-9α-fluoro-5α-androstane (1.02 g), which crystallised from hexane as prisms (917 mg) m.p. 140°-142°; [α] D24 -22° (c 1.47, CHCl3). (Found C,55.10; H,5.78; F,26.35%;m/e 502. C33H29O4F7 requires C,54.97; H,5.82; F,26.47%; M+ 502).

Aufarbeitung

  1. customThereafter the solution was purged with nitrogen
  2. customthe solvent was removed in vacuo
  3. dissolutionThe residue was dissolved in chloroform
  4. washthe resulting solution was washed with aqueous sodium bicarbonate and water
  5. customwas then dried, whereafter the product
  6. customwas chromatographed on silica gel (125 g)
  7. washElution with chloroform:hexane (3:7)
  8. customgave unreacted
  9. washwhile subsequent elution with chloroform:hexane (7:13)

Quellen und Nachweise

ORD-Eintrag
ord-d677881fb3ef4d35b175ab87e500a362
Quelldatensatz
uspto-grants-1981_08
Patentnummer
US04284558

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