Iodine → HCID 53924134, compound

HRID 326491Notes

Reaction equation

HRID 326491 reaction equation
[OH:1][C@@H:2]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[C@@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:18]2[CH2:17][CH2:16][C@@:15]2([CH3:23])[C@H:8]3[CH2:9][C@@H:10]([CH3:24])[C@@H:11]2[C:12](=[O:14])[CH3:13])[CH2:3]1.C(Cl)(Cl)(Cl)Cl.[O-2].[Ca+2].[I:32]I>CO.[Cl-].[Ca+2].[Cl-].C1COCC1>[OH:1][C@@H:2]1[CH2:21][CH2:20][C@@:19]2([CH3:22])[C@@H:4]([CH2:5][CH2:6][C@@H:7]3[C@@H:18]2[CH2:17][CH2:16][C@@:15]2([CH3:23])[C@H:8]3[CH2:9][C@@H:10]([CH3:24])[C@@H:11]2[C:12](=[O:14])[CH2:13][I:32])[CH2:3]1

Participants

8

Reactant 4

HCID 807IodineHCID 5943Carbon TetrachlorideHCID 6850728CalciumoxideHCID 53719857HCID 53719857, compound

Product 1

HCID 53924134HCID 53924134, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 5284359Calcium ChlorideSolvent2×

Procedure

A mixture of 3α-hydroxy-16α-methyl-5α-pregnan-20-one (21 g) methanol (80 ml), carbon tetrachloride (40 ml), THF (120 ml), calcium oxide (25 g) and calcium chloride in methanol (10%, 3 ml) is stirred at 25°-30°. A solution of iodine (20 g) in calcium chloride (10%, 70 ml) is added to the steroid mixture over 1 hr. The mixture is stirred an additional 2 hr at 30°, filtered through a pad of filter aid, and the filtrate concentrated under reduced pressure to an oil. The oil is dissolved in methylene chloride and flash chromatographed over silica gel (100 g) eluting with methylene chloride/ethyl acetate (4/1). The appropriate fractions are pooled, concentrated and the residue triturated with ether to give the title compound.

Workup

  1. stirringThe mixture is stirred an additional 2 hr at 30°
  2. filtrationfiltered through a pad of filter aid
  3. concentrationthe filtrate concentrated under reduced pressure to an oil
  4. dissolutionThe oil is dissolved in methylene chloride
  5. customflash chromatographed over silica gel (100 g)
  6. washeluting with methylene chloride/ethyl acetate (4/1)
  7. concentrationconcentrated
  8. customthe residue triturated with ether

Sources & evidence

ORD record
ord-8da3ab01dd7c4cc79ba58dc25de1dee6
Source dataset
uspto-grants-1993_12
Patent number
US05268477

Reaction notes

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