Sodium Iodide → HCID 18600757, compound

HRID 652215Notes

Reaction equation

HRID 652215 reaction equation
C1C=C[NH+]=CC=1.[Br:7][Br-]Br.[CH2:10]1[CH2:34][O:33][C:12]2([CH2:17][CH2:16][C@H:15]3[C@H:18]4[C@H:28]([C@@H:29]([OH:31])[CH2:30][C@:13]23[CH3:14])[C@:26]2([CH3:27])[C:21]([CH2:22][C@@H:23]([OH:32])[CH2:24][CH2:25]2)=[CH:20][CH2:19]4)[O:11]1.[I-].[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>O1CCCC1.O.N1C=CC=CC=1>[Br:7][C@@H:17]1[CH2:16][C@H:15]2[C@H:18]3[C@H:28]([C@@H:29]([OH:31])[CH2:30][C@:13]2([CH3:14])[C:12]21[O:11][CH2:10][CH2:34][O:33]2)[C@:26]1([CH3:27])[C:21]([CH2:22][C@@H:23]([OH:32])[CH2:24][CH2:25]1)=[CH:20][CH2:19]3

Participants

7

Reactant 3

HCID 5238Sodium IodideHCID 24477Sodium ThiosulfateHCID 14238053HCID 14238053, compound

Product 1

HCID 18600757HCID 18600757, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Procedure

36.3 g of pyridine hydrobromide perbromide are added to a solution of 16.8 g of 17,17-ethylenedioxyandrost-5-ene-3β,11β-diol in 102 ml of tetrahydrofuran and the whole is stirred at room temperature for 21/2 hours. 26.9 g of sodium iodide are added to the mixture, which is then stirred for a further 30 minutes; a solution of 36.3 g of sodium thiosulphate in 50.4 ml of water, and 100 ml of pyridine are added in succession to the mixture and stirring is continued for a further 2 hours at room temperature. The reaction mixture is diluted with 100 ml of water and concentrated under a water-jet vacuum at approximately 45°. The residue is taken up in ethyl acetate and washed in succession with saturated sodium chloride solution, ice-cold dilute hydrochloric acid, ice-cold dilute sodium hydroxide solution and again with saturated sodium chloride solution and dried over sodium sulphate. Distilling off the solvent under a water-jet vacuum results in an amorphous residue comprising crude 16α-bromo-17,17-ethylenedioxyandrost-5-ene-3β, 11β-diol. The resulting crude product (13 g) is dissolved in 143 ml of dimethyl sulphoxide, and, while stirring, a mixture of 7 g of potassium tert.-butoxide in 13 ml of dimethyl sulphoxide is added at 45° in the course of 30 minutes and stirring is continued for 20 hours at 50° (bath temperature). The mixture is cooled to room temperature, diluted with approximately 1300 ml of a saturated ammonium chloride solution and taken up in ethyl acetate; the organic phase is washed three times with saturated sodium chloride solution and dried over sodium sulphate. By distilling off the solvent under a water-jet vacuum there is obtained amorphous 17,17-ethylenedioxyandrosta-5,15-diene-3β,11β-diol of a purity adequate for further processing.

Workup

  1. stirringis then stirred for a further 30 minutes
  2. stirringstirring
  3. waitis continued for a further 2 hours at room temperature
  4. concentrationconcentrated under a water-jet vacuum at approximately 45°
  5. washwashed in succession with saturated sodium chloride solution, ice-cold dilute hydrochloric acid, ice-cold dilute sodium hydroxide solution and again with saturated sodium chloride solution
  6. dry with materialdried over sodium sulphate
  7. distillationDistilling off the solvent under a water-jet vacuum

Sources & evidence

ORD record
ord-8a1986d5b21d4f37a8164de163d2a009
Source dataset
uspto-grants-1987_06
Patent number
US04670551

Reaction notes

Loading…