Hydrochloric Acid → HCID 15292241, compound

HRID 1449482Notes

Reaction equation

HRID 1449482 reaction equation
[OH:1]/[N:2]=[CH:3]/[C@H:4]1[CH2:9][CH2:8][C@:7]2([OH:24])[C@H:10]3[C@H:20]([CH2:21][CH2:22][C@:5]12[CH3:6])[C@:18]1([CH3:19])[C@@H:13]([CH2:14][C@@H:15]([OH:23])[CH2:16][CH2:17]1)[CH2:12][CH2:11]3.Cl.[BH3-]C#N.[Na+].[OH-].[Na+]>CO>[OH:1][NH:2][CH2:3][C@H:4]1[CH2:9][CH2:8][C@:7]2([OH:24])[C@H:10]3[C@H:20]([CH2:21][CH2:22][C@:5]12[CH3:6])[C@:18]1([CH3:19])[C@@H:13]([CH2:14][C@@H:15]([OH:23])[CH2:16][CH2:17]1)[CH2:12][CH2:11]3

Participants

6

Reactant 4

HCID 313Hydrochloric Acid2×HCID 14798Sodium HydroxideHCID 5003444Sodium cyanoborohydride2×HCID 9819105(3S,5R,8R,9S,10S,13R,14S,17S)-17-[(E)-hydroxyiminomethyl]-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,14-diol

Product 1

HCID 15292241HCID 15292241, compoundYield 74.6%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

A stirred solution of 0.60 g of (E)-17β-hydroxyiminomethyl-5β-androstane-3β,14β-diol (prepared following the procedure described in DE 4,227,605 for similar compounds) in 6 ml of methanol was acidified to pH 3 with 1N HCl. 0.30 g of NaBH3CN were added and 0.1N HCl was continuously added, by means of a pH-stat, to maintain pH 2.8+3.0. After 6 hr, 0.15 g of NaBH3CN were added and the reaction was left on stirring overnight. The solution was basified to pH 10 with 2.5N NaOH and methanol was evaporated under reduced pressure. The mixture was extracted with ethyl acetate; the organic layer was dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The residue was purified by flash-chromatography (SiO2) using cyclohexane/ethyl acetate 20/80 as the eluant; the fractions containing the title compound were collected and evaporated to dryness under reduced pressure. The residue was dissolved with diethyl ether/ethyl acetate and the solution was added with the stoichiometric amount of oxalic acid to give 0.45 g of the title compound (I-ah), as a white solid, oxalate.

Workup

  1. temperatureto maintain pH 2.8+3.0
  2. waitthe reaction was left
  3. customwas evaporated under reduced pressure
  4. extractionThe mixture was extracted with ethyl acetate
  5. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  6. customevaporated to dryness under reduced pressure
  7. customThe residue was purified by flash-chromatography (SiO2)
  8. additionthe fractions containing the title compound
  9. customwere collected
  10. customevaporated to dryness under reduced pressure
  11. dissolutionThe residue was dissolved with diethyl ether/ethyl acetate
  12. additionthe solution was added with the stoichiometric amount of oxalic acid

Sources & evidence

ORD record
ord-40743b1a76d84af680e5cdf93468e819
Source dataset
uspto-grants-1997_02
Patent number
US05599806

Reaction notes

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