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

HRID 1650785노트

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HRID 1650785 반응식
[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

참가 물질

7

반응물 4

HCID 962WaterHCID 14614219-Thiomethylandrost-4-ene-3,17-dioneHCID 197823(Chloromethyl)triphenylphosphonium chlorideHCID 178418339Butyllithium

생성물 1

HCID 545684673-Chloromethylene-19-methylthio-4-androsten-17-one수율 49.7%

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매

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온도
0 °C

실험 절차

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.

후처리

  1. extractionextracted three times with ethyl acetate
  2. washwashed neutral
  3. customdried on sodium sulfate
  4. concentrationconcentrated to dryness
  5. custom995 mg of raw product is obtained
  6. customwhich after chromatographic purification

출처 및 근거

ORD 기록
ord-c2c3cbc1c3e34d9fb391d0b27f0343a3
출처 데이터셋
uspto-grants-1990_05
특허 번호
US04925834

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