19-Mercaptoandrost-4-ene-3,17-dione → 3-Fluoromethylene-19-mercapto-4-androsten-17-one

HRID 1650790ノート

反応式

HRID 1650790 の反応式
F[B-](F)(F)F.[F:6][CH2:7][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CC([O-])(C)C.[K+].[SH:33][CH2:34][C@@:35]12[C@@H:52]3[C@H:43]([C@H:44]4[C@@:48]([CH2:50][CH2:51]3)([CH3:49])[C:47](=[O:53])[CH2:46][CH2:45]4)[CH2:42][CH2:41][C:40]1=[CH:39][C:38](=O)[CH2:37][CH2:36]2>O1CCCC1.Cl>[F:6][CH:7]=[C:38]1[CH2:37][CH2:36][C@@:35]2([CH2:34][SH:33])[C:40]([CH2:41][CH2:42][C@@H:43]3[C@@H:52]2[CH2:51][CH2:50][C@@:48]2([CH3:49])[C@H:44]3[CH2:45][CH2:46][C:47]2=[O:53])=[CH:39]1

参加物

6

反応物 3

HCID 14614119-Mercaptoandrost-4-ene-3,17-dioneHCID 11303586(Fluoromethyl)triphenylphosphonium tetrafluoroborateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 540614093-Fluoromethylene-19-mercapto-4-androsten-17-one収率 47.7%

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

17.2 g of fluoromethyl triphenylphosphonium tetrafluoroborate is suspended in 120 ml of tetrahydrofuran and mixed at 25° C. by portions with 7.8 g of potassium tert-butylate. Stirring is continued for one more hour, it is cooled to 0° C. and 1.5 g of 19-mercapto-4-androstene-3,17-dione (European patent 100,556) is instilled in 10 ml of tetrahydrofuran and stirring is continud for 30 more minutes. Then it is neutralized in 1N hydrochloric acid, the reaction mixture is added to waer, extracted 4 times with ethyl acetate, the organic phases washed neutral, dried on sodium sulfate and freed rom the solvent in a vacuum. After chromatography on silica gel with hexane/ethyl acetate, 752 mg of 3-fluoromethylene-19-mercapto-4-androsten-17-one with a melting point of 118°-120° C. is obtained.

後処理

  1. stirringstirring
  2. additionthe reaction mixture is added to waer
  3. extractionextracted 4 times with ethyl acetate
  4. washthe organic phases washed neutral
  5. customdried on sodium sulfate

出典と根拠

ORDレコード
ord-1e8d401049194e2e9210c36950f06ec5
出典データセット
uspto-grants-1990_05
特許番号
US04925834

反応ノート

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