Equilin → 17-Methylenestra-1,3,5(10),7-tetraen-3-ol

HRID 1781946ノート

反応式

HRID 1781946 の反応式
[CH3:1]C(C)([O-])C.[K+].[CH3:7][C@@:8]12[C:24](=O)[CH2:23][CH2:22][C@H:21]1[C:20]1[C@@H:11]([C:12]3[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=3[CH2:18][CH:19]=1)[CH2:10][CH2:9]2>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CS(C)=O>[CH2:1]=[C:24]1[CH2:23][CH2:22][C@H:21]2[C:20]3[C@H:11]([CH2:10][CH2:9][C@:8]12[CH3:7])[C:12]1[CH:13]=[CH:14][C:15]([OH:26])=[CH:16][C:17]=1[CH2:18][CH:19]=3

参加物

5

反応物 2

HCID 223368EquilinHCID 23665647Potassium tert-butoxide

生成物 1

HCID 2287307017-Methylenestra-1,3,5(10),7-tetraen-3-ol

試薬・触媒・溶媒 2

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 679Dimethyl Sulfoxide溶媒2 回

実験手順

Methyltriphenylphosphonium bromide (1.9967 g, 5.5892 mmol) and potassium t-butoxide (627.2 mg, 5.589 mmol) suspended in 6.1 mL of anh. DMSO under argon were 1 h in an oil bath (71°-83° C., after which equilin (300.0 mg, 1.118 mmol) in 6.1 μL of anh. DMSO was added via syringe. See FIG. 18. After stirring a further 70 min., the reaction mixture was poured into 40 mL of ice water and extracted three times with 25 mL portions of ether. The combined organic extracts were washed with 25 mL of brine, dried over magnesium sulfate, and filtered through diatomaceous earth. The residue was washed with 10 mL of ether and the combined filtrates were concentrated under reduced pressure. Flash chromatography (15% ethyl acetate/hexanes on silica gel) followed by preparative TLC (20% ethyl acetate/hexanes on silica gel GF, 1000μ thickness) gave an opaque white film (162.3 mg, 0.6093 mmol, 54%). (NA)-1994A-258)

後処理

  1. extractionextracted three times with 25 mL portions of ether
  2. washThe combined organic extracts were washed with 25 mL of brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered through diatomaceous earth
  5. washThe residue was washed with 10 mL of ether
  6. concentrationthe combined filtrates were concentrated under reduced pressure
  7. customgave an opaque white film (162.3 mg, 0.6093 mmol, 54%)

出典と根拠

ORDレコード
ord-0e8369bf0a9a4d91adb66baad07b17e0
出典データセット
uspto-grants-1997_05
特許番号
US05633392

反応ノート

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