Acetic Anhydride → 3beta-Acetoxy-9alpha-fluoro-17alpha-hydroxy-16beta-methyl-5alpha-pregnan-20-one

HRID 259223

反応式

HRID 259223 の反応式
[C:1]([O:4][C@H:5]1[CH2:24][CH2:23][C@@:22]2([CH3:25])[C@@H:7]([CH2:8][CH2:9][C@@H:10]3[C@@H:21]2[CH2:20][CH2:19][C@@:18]2([CH3:26])[C@H:11]3[CH2:12][C@H:13]([CH3:28])[C@:14]2([OH:27])[C:15](=[O:17])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2].C(OC(=O)C)(=O)C.[F:36]C(F)(F)C([O-])=O.[Na+].FF.S([O-])([O-])(=O)=S.[Na+].[Na+]>N1C=CC=CC=1.FC(Cl)(Cl)Cl.C(Cl)(Cl)Cl>[C:1]([O:4][C@H:5]1[CH2:24][CH2:23][C@@:22]2([CH3:25])[C@@H:7]([CH2:8][CH2:9][C@@H:10]3[C@:21]2([F:36])[CH2:20][CH2:19][C@@:18]2([CH3:26])[C@H:11]3[CH2:12][C@H:13]([CH3:28])[C@:14]2([OH:27])[C:15](=[O:17])[CH3:16])[CH2:6]1)(=[O:3])[CH3:2]

参加物

9

反応物 5

HCID 7918Acetic AnhydrideHCID 24477Sodium ThiosulfateHCID 24524Fluorine2 回HCID 517019Sodium Trifluoroacetate2 回HCID 705695903beta-Acetoxy-17alpha-hydroxy-16beta-methyl-5alpha-pregnan-20-one

生成物 1

HCID 705714633beta-Acetoxy-9alpha-fluoro-17alpha-hydroxy-16beta-methyl-5alpha-pregnan-20-one収率 50%

試薬・触媒・溶媒 3

HCID 1049Pyridine溶媒HCID 6212Chloroform溶媒HCID 6389Trichlorofluoromethane溶媒

実験手順

3β-Acetoxy-17α-hydroxy-16β-methyl-5α-pregnan-20-one (1g, prepared by treatment of the corresponding 3β-ol with acetic anhydride in pyridine) was dissolved in fluorotrichloromethane (250 ml) and chloroform (200 ml) containing sodium trifluoroacetate (ca. 2g) and sodium fluoride (ca. 2g). The resulting solution was cooled to -78° and vigourously stirred, whereupon fluorine from four 750 cc bottles (8-10% v/v fluorine in nitrogen) was added over 9-10 hours. The reaction solution was then poured into aqueous sodium thiosulphate and the organic layer was separated, washed with water, dried over potassium carbonate and evaporated to dryness. The residue was purified by liquid chromatography, eluting with cyclohexane containing 30% v/v ethyl acetate and 0.1% v/v pyridine, to yield 3β-acetoxy-9α-fluoro-17α-hydroxy-16β-methyl-5α-pregnan-20-one (50%); m.p. 150° (after recrystallisation from acetone); PMR spectrum includes signals at δ 2.20 (21-Me), 2.00 (3-0.CO.CH3), 0.92 (19-Me) and 0.87 (18-Me); FMR φ* + 179.5 ppm. (Found: C, 70.51; H, 9.20; F, 4.48; C24H37FO4 requires C, 70.55; H, 9.13; F, 4.65%).

後処理

  1. temperatureThe resulting solution was cooled to -78°
  2. additionwas added over 9-10 hours
  3. customthe organic layer was separated
  4. washwashed with water
  5. dry with materialdried over potassium carbonate
  6. customevaporated to dryness
  7. customThe residue was purified by liquid chromatography
  8. washeluting with cyclohexane containing 30% v/v ethyl acetate and 0.1% v/v pyridine

出典と根拠

ORDレコード
ord-341cd432a5774b1abdb3ca24085de1b0
出典データセット
uspto-grants-1977_07
特許番号
US04036864

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