Ammonium Chloride → 3-Fluoromethylene-19-methylthio-4-androsten-17-one

HRID 1650786Notes

Reaction equation

HRID 1650786 reaction equation
[CH3:1][S:2][CH2:3][C@@:4]12[C@@H:21]3[C@H:12]([C@H:13]4[C@@:17]([CH2:19][CH2:20]3)([CH3:18])[C:16](=[O:22])[CH2:15][CH2:14]4)[CH2:11][CH2:10][C:9]1=[CH:8][C:7](=O)[CH2:6][CH2:5]2.F[B-](F)(F)F.[F:29][CH2:30][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.[Cl-].[NH4+]>C(COC)OC.O>[F:29][CH:30]=[C:7]1[CH2:6][CH2:5][C@@:4]2([CH2:3][S:2][CH3:1])[C:9]([CH2:10][CH2:11][C@@H:12]3[C@@H:21]2[CH2:20][CH2:19][C@@:17]2([CH3:18])[C@H:13]3[CH2:14][CH2:15][C:16]2=[O:22])=[CH:8]1

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 14614219-Thiomethylandrost-4-ene-3,17-dioneHCID 11303586(Fluoromethyl)triphenylphosphonium tetrafluoroborateHCID 178418339Butyllithium

Product 1

HCID 536819483-Fluoromethylene-19-methylthio-4-androsten-17-one

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

500 ml of 19-methylthio-4-androsten-3,17-dione (Euoprean patent 100,566) in 10 ml of dimethoxyethane is added drop by drop at 0° C. to a suspension of 5.73 g of fluoromethyl triphenylphosphonium tetrafluoroborate in 40 ml of dimethoxyethane, which was stirred with 9.5 ml of butyllithium solution (1.6 m in ether) for 0.5 hour, instilled and stirred for another 15 minutes. Then saturated ammonium chloride solution is added, diluted with water, extracted three times with ethyl acetate, washed neutral, dried on sodium sulfate and concentrated in a vacuum. After chromatography on silica gel with hexane/ethyl acetate, 331 mg of pure 3-fluoromethylene-19-methylthio-4-androsten-17-one with a melting point of 146°-147° C. [α]D +288.4° (CHCl3) as E:Z mixture is obtained.

Workup

  1. extractionextracted three times with ethyl acetate
  2. washwashed neutral
  3. customdried on sodium sulfate
  4. concentrationconcentrated in a vacuum

Sources & evidence

ORD record
ord-88bbf6e46244461ba746550bf69e2cea
Source dataset
uspto-grants-1990_05
Patent number
US04925834

Reaction notes

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