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

HRID 1650785ノート

反応式

HRID 1650785 の反応式
[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

参加物

7

反応物 4

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

生成物 1

HCID 545684673-Chloromethylene-19-methylthio-4-androsten-17-one収率 49.7%

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-c2c3cbc1c3e34d9fb391d0b27f0343a3
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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