Aluminium lithium hydride → HCID 14238053, compound

HRID 652214Notes

Reaction equation

HRID 652214 reaction equation
C([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:19]2[C@@H:18]([O:24]C(=O)C)[CH2:17][C@@:15]2([CH3:16])[C@H:11]3[CH2:12][CH2:13][C:14]32[O:31][CH2:30][CH2:29][O:28]3)[CH2:6]1)(=O)C.[H-].[Al+3].[Li+].[H-].[H-].[H-]>O1CCCC1>[CH2:30]1[CH2:29][O:28][C:14]2([CH2:13][CH2:12][C@H:11]3[C@H:10]4[C@H:19]([C@@H:18]([OH:24])[CH2:17][C@:15]23[CH3:16])[C@:20]2([CH3:23])[C:7]([CH2:6][C@@H:5]([OH:4])[CH2:22][CH2:21]2)=[CH:8][CH2:9]4)[O:31]1

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 54235031HCID 54235031, compound

Product 1

HCID 14238053HCID 14238053, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

At an internal temperature of 5°-10°, a solution of 4.7 g of 3β,11β-diacetoxy-17,17-ethylenedioxyandrost-5-ene in 140 ml of tetrahydrofuran is added dropwise to a stirred suspension of 2.35 g of lithium aluminium hydride in 95 ml of tetrahydrofuran and then rinsed out with 9 ml of tetrahydrofuran, and the mixture is boiled under reflux for 12 hours. The reaction mixture is decomposed at an internal temperature of a maximum of 5° by the careful dropwise addition of a mixture of 9 ml of tetrahydrofuran and 14 ml of ethyl acetate followed by a mixture of 9 ml of tetrahydrofuran and 14 ml of water, and after the addition of 70 g of anhydrous sodium sulphate the mixture is stirred without cooling for a further 30 minutes. Solid portions are removed by filtration with suction over a layer of kieselguhr (subsequent washing with tetrahydrofuran) and the filtrate is concentrated under a water-jet vacuum. The amorphous residue is chromatographed over 50 times the amount by weight of silica gel. Elution with a mixture of methylene chloride/acetone (93:7) and evaporation of the solvent yield uniform 17,17-ethylenedioxyandrost-5-ene-3β,11β-diol which, after being dissolved and recrystallised once from methylene chloride/ether, melts at 123°-125°.

Workup

  1. washrinsed out with 9 ml of tetrahydrofuran
  2. temperatureunder reflux for 12 hours
  3. additionThe reaction mixture is decomposed at an internal temperature of a maximum of 5° by the careful dropwise addition of a mixture of 9 ml of tetrahydrofuran and 14 ml of ethyl acetate
  4. additionfollowed by a mixture of 9 ml of tetrahydrofuran and 14 ml of water
  5. additionafter the addition of 70 g of anhydrous sodium sulphate the mixture
  6. temperaturewithout cooling for a further 30 minutes
  7. customSolid portions are removed by filtration with suction over a layer of kieselguhr (subsequent washing with tetrahydrofuran)
  8. concentrationthe filtrate is concentrated under a water-jet vacuum
  9. customThe amorphous residue is chromatographed over 50 times the amount by weight of silica gel
  10. washElution
  11. additionwith a mixture of methylene chloride/acetone (93:7) and evaporation of the solvent

Sources & evidence

ORD record
ord-f4906a33300042ee819a1135f833755c
Source dataset
uspto-grants-1987_06
Patent number
US04670551

Reaction notes

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