Water → 3-Chloromethylene-19-methylthio-4-androsten-17-one

HRID 1650785Notes

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.[Cl-].[Cl:25][CH2:26][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.O>O1CCCC1.CCOCC>[Cl:25][CH:26]=[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

Conditions

Temperature: 0 °C

Procedure

500 mg of 19-methylthio-4-androstene-3,17-dione (European patent 100,566) is added to a suspension of 5.21 g of chloromethyl triphenylphosphonium chloride in 50 ml of tetrahydrofuran, which was stirred with 9.5 ml of (1.6 m of butyllithium in ether) 0.5 hours at 20° C., and stirred for 30 minutes at 0° C. Then it is mixed with water, extracted three times with ethyl acetate, washed neutral, dried on sodium sulfate and concentrated to dryness. 995 mg of raw product is obtained, which after chromatographic purification yields 273 mg of pure 3-chloromethylene-19-methylthio-4-androsten-17-one with a melting point of 114°-115° C., [α]D +241.5° C. (CHCl3), as pure E form.

Workup

extractionextracted three times with ethyl acetate
washwashed neutral
customdried on sodium sulfate
concentrationconcentrated to dryness
custom995 mg of raw product is obtained
customwhich after chromatographic purification

Sources & evidence

ORD record: ord-c2c3cbc1c3e34d9fb391d0b27f0343a3
Source dataset: uspto-grants-1990_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04925834

Reaction notes

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