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

HRID 1650790Notes

Reaction equation

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

Participants

Conditions

Temperature: 0 °C

Procedure

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.

Workup

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

Sources & evidence

ORD record: ord-1e8d401049194e2e9210c36950f06ec5
Source dataset: uspto-grants-1990_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04925834

Reaction notes

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