Ammonium Chloride → Cholesta-5,7-diene-1,3-diol

HRID 1587630Notes

Reaction equation

HRID 1587630 reaction equation
[CH3:1][CH:2]([C@@H:15]1[C@:32]2([CH3:33])[C@H:18]([C:19]3[C@H:29]([CH2:30][CH2:31]2)[C@:27]2([CH3:28])[C:22]([CH2:23][C@@H:24]([O:42][Si](C(C)(C)C)(C)C)[CH2:25][C@@H:26]2[O:34][Si](C(C)(C)C)(C)C)=[CH:21][CH:20]=3)[CH2:17][CH2:16]1)[CH2:3]OS(C1C=CC(C)=CC=1)(=O)=O.[I-].[CH2:51]([Li])[CH2:52][CH:53]([CH3:55])[CH3:54].[Cl-].[NH4+]>C(OCC)C>[CH3:54][CH:53]([CH2:52][CH2:51][CH2:3][C@H:2]([C@@H:15]1[C@:32]2([CH3:33])[C@H:18]([C:19]3[C@H:29]([CH2:30][CH2:31]2)[C@:27]2([CH3:28])[C:22]([CH2:23][C@@H:24]([OH:42])[CH2:25][C@@H:26]2[OH:34])=[CH:21][CH:20]=3)[CH2:17][CH2:16]1)[CH3:1])[CH3:55]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 30165Iodide IonHCID 8674694620-Methyl-1alpha,3beta-bis(t-butyldimethylsilyloxy)-21-p-toluenesulfonyloxypregna-5,7-dieneHCID 178506862HCID 178506862, compound

Product 1

HCID 193829Cholesta-5,7-diene-1,3-diol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent4×

Conditions

Temperature
-30 °C

Procedure

A solution of 99 mg of 20-methyl-1α,3β-bis(t-butyldimethylsilyloxy)-21-p-toluenesulfonyloxypregna-5,7 -diene in 2 ml of diethyl ether was added dropwise, at -50° C. to -60° C., to a diethyl ether solution of iodide and 0.9 ml of a 1.1N diethyl ether solution of isoamyllithium in 2 ml of diethyl ether. After stirring at -30° C. for 1 hour, the reaction mixture was poured into a cold aqueous solution of ammonium chloride, followed by extraction with diethyl ether. The extract was washed with 10% aqueous ammonia, water and an aqueous solution of sodium chloride, dried over sodium sulfate and concentrated. The residue was dissolved in 2 ml of tetrahydrofuran, 1 ml of a 40% aqueous solution of tetra-n-butylammonium fluoride was added, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was diluted with water and extracted with methylene chloride. The extract was washed with an aqueous solution of sodium chloride, dried over sodium sulfate and concentrated. The residue was washed with cold ethyl acetate to give 45 mg of cholesta-5,7-diene-1α,3β-diol, whose 1H NMR spectrum was identical with that obtained in Reference Example 8.

Workup

  1. extractionfollowed by extraction with diethyl ether
  2. washThe extract was washed with 10% aqueous ammonia, water
  3. dry with materialan aqueous solution of sodium chloride, dried over sodium sulfate
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in 2 ml of tetrahydrofuran
  6. addition1 ml of a 40% aqueous solution of tetra-n-butylammonium fluoride was added
  7. stirringthe mixture was stirred at room temperature for 6 hours
  8. additionThe reaction mixture was diluted with water
  9. extractionextracted with methylene chloride
  10. washThe extract was washed with an aqueous solution of sodium chloride
  11. dry with materialdried over sodium sulfate
  12. concentrationconcentrated
  13. washThe residue was washed with cold ethyl acetate

Sources & evidence

ORD record
ord-2da34978abc04fd694a3c0b12f9d4fcb
Source dataset
uspto-grants-1993_06
Patent number
US05218109

Reaction notes

Loading…