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

HRID 259219

反応式

HRID 259219 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

HCID 867349613beta,17beta-Di(trifluoroacetoxy)-9alpha-fluoro-5alpha-androstane収率 39.4%

試薬・触媒・溶媒 1

HCID 6389Trichlorofluoromethane溶媒

実験手順

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 crystallized from hexane as prisms (917 mg) m.p. 140°-142°; [α] 24D - 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).

後処理

  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)

出典と根拠

ORDレコード
ord-50793cc9a5b34832bb6f4dd45901331d
出典データセット
uspto-grants-1977_07
特許番号
US04036864

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