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

HRID 1587629Notes

Reaction equation

HRID 1587629 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:38]C(=O)C)[CH2:25][C@@H:26]2[O:34]C(=O)C)=[CH:21][CH:20]=3)[CH2:17][CH2:16]1)[CH2:3]OS(C1C=CC(C)=CC=1)(=O)=O.[Li].C([Cu]CCC(C)C)CC(C)C.[CH2:54]([Li])[CH2:55][CH:56]([CH3:58])[CH3:57].[Cl-].[NH4+]>C(OCC)C>[CH3:57][CH:56]([CH2:55][CH2:54][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:38])[CH2:25][C@@H:26]2[OH:34])=[CH:21][CH:20]=3)[CH2:17][CH2:16]1)[CH3:1])[CH3:58]

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 8674694520-Methyl-1alpha,3beta-diacetoxy-21-p-toluenesulfonyloxypregna-5,7-dieneHCID 178445856HCID 178445856, compoundHCID 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 82 mg of 20-methyl-1α,3β-diacetoxy-21-p-toluenesulfonyloxypregna-5,7-diene in 1.5 ml of diethyl ether was added dropwise, at -50° C. to -60° C., to a diethyl ether solution of diisoamylcopper lithium prepared from 100 mg of cuprous 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 1 ml of methanol, 10 mg of potassium carbonate was added, and the mixture was stirred at ambient temperature for 10 hours. Thereafter, the isolation and purification procedure of Reference Example 8 was repeated to give 35 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 1 ml of methanol
  6. addition10 mg of potassium carbonate was added
  7. stirringthe mixture was stirred at ambient temperature for 10 hours
  8. customThereafter, the isolation and purification procedure of Reference Example 8

Sources & evidence

ORD record
ord-c8ccfe530c68493a8da932d4aeeed9be
Source dataset
uspto-grants-1993_06
Patent number
US05218109

Reaction notes

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