Water → HCID 22846461, compound

HRID 2254553Notes

Reaction equation

HRID 2254553 reaction equation
[CH2:1]1[S:24][C:4]2([CH2:21][CH2:20][C@H:19]3[C:6]([CH2:7][CH2:8][C@@H:9]4[C@@H:18]3[C:17](=[CH2:22])[CH2:16][C@@:14]3([CH3:15])[C@H:10]4[CH:11]=[CH:12][C:13]3=[O:23])=[CH:5]2)[S:3][CH2:2]1.[K].O.[Na+].[Cl-].O1CC[CH2:31][CH2:30]1>C#C>[CH2:2]1[S:3][C:4]2([CH2:21][CH2:20][C@H:19]3[C:6]([CH2:7][CH2:8][C@@H:9]4[C@@H:18]3[C:17](=[CH2:22])[CH2:16][C@@:14]3([CH3:15])[C@H:10]4[CH:11]=[CH:12][C@:13]3([C:30]#[CH:31])[OH:23])=[CH:5]2)[S:24][CH2:1]1

Participants

7

Reactant 5

HCID 962Water2×HCID 5234Sodium ChlorideHCID 8028Tetrahydrofuran3×HCID 5462222PotassiumHCID 22846463HCID 22846463, compound

Product 1

HCID 22846461HCID 22846461, compound

Reagents, catalysts & solvents 1

HCID 6326AcetyleneSolvent2×

Procedure

A solution of 3.5 g of 11-methylene-oestr-4,15-diene-3,17-dione-3-ethylenedithioacetal in 52.5 ml of dry tetrahydrofuran was added, at -15° C. to -20° C., with stirring, to a tetrahydrofuran solution of potassium acetalide, prepared from 8.4 g of potassium tert.-butylate in acetylene. The reaction mixture was stirred for a further hour at this temperature, with continuous passage of acetylene. Thereafter, a mixture of 10 ml of water and 10 ml of tetrahydrofuran was added dropwise to the reaction mixture at -15° C. to -20° C. The reaction mixture was then poured out into a mixture of 1 liter of saturated NaCl solution and 0.5 liter of water. The precipitate was filtered off, washed neutral with water and dried in vacuo. After purification by chromatography over silica gel and crystallisation from diethyl ether/hexane, 2.6 g of 11-methylene-17α-ethinyl-17β-hydroxy-oestra-4,15-diene-3-one-3-ethylenedithioacetal were obtained, melting point 170.5° C.; [α] D20 =-21 (chloroform, c=1%).

Workup

  1. additionwas added dropwise to the reaction mixture at -15° C. to -20° C
  2. filtrationThe precipitate was filtered off
  3. washwashed neutral with water
  4. customdried in vacuo
  5. customAfter purification by chromatography
  6. customover silica gel and crystallisation from diethyl ether/hexane

Sources & evidence

ORD record
ord-6a9bb6734dac427ab355769d5ff4dd19
Source dataset
uspto-grants-1993_08
Patent number
US05236913

Reaction notes

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