Sodium Bicarbonate → (3S,5R,8R,9S,10S,13R,14S,17S)-17-[(E)-methoxyiminomethyl]-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,14-diol

HRID 1757085Notes

Reaction equation

HRID 1757085 reaction equation
Cl.[O:2]([NH2:4])[CH3:3].C([O-])(O)=O.[Na+].[OH:10][C@H:11]1[CH2:28][CH2:27][C@@:26]2([CH3:29])[C@H:13]([CH2:14][CH2:15][C@@H:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@:17]3([OH:32])[CH2:18][CH2:19][C@@H:20]2[CH:30]=O)[CH2:12]1>O1CCOCC1.O>[CH3:3][O:2]/[N:4]=[CH:30]/[C@H:20]1[CH2:19][CH2:18][C@:17]2([OH:32])[C@H:16]3[C@H:25]([CH2:24][CH2:23][C@:21]12[CH3:22])[C@:26]1([CH3:29])[C@@H:13]([CH2:12][C@@H:11]([OH:10])[CH2:28][CH2:27]1)[CH2:14][CH2:15]3

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 521874O-Methylhydroxylamine hydrochlorideHCID 109033043beta,14beta-Dihydroxy-5beta-androstane-17beta-carboxaldehyde

Product 1

HCID 10665493(3S,5R,8R,9S,10S,13R,14S,17S)-17-[(E)-methoxyiminomethyl]-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,14-diolYield 36.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

To a suspension of 0.16 g of methoxylamine hydrochloride and 0.19 g of NaHCO3 in 12 ml of dioxane and 10 ml of water a solution of 0.50 g of 3β,14β-dihydroxy-5β-androstane-17β-carboxaldehyde (Boutagy J. and Thomas R., Aust. J. Chem., 1971, 24, 2723) in 6 ml of dioxane was added dropwise at room temperature. After 15 minutes the solution was diluted with water and extracted with chloroform; the organic layer was dried over anhydrous sodium sulfate and evaporated to dryness. The crude product was purified by flash-chromatography (SiO2) using cyclohexane/ethyl acetate 60/40; the fractions containing the rifle compound were collected and evaporated to dryness. The residue was ground with di-iso-propyl ether/ethanol to give 0.20 g of the title compound (I-aa), as a white solid.

Workup

  1. additionwas added dropwise at room temperature
  2. extractionextracted with chloroform
  3. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  4. customevaporated to dryness
  5. customThe crude product was purified by flash-chromatography (SiO2)
  6. additionthe fractions containing the rifle compound
  7. customwere collected
  8. customevaporated to dryness

Sources & evidence

ORD record
ord-f76936392df4464c81c84f28e93a2df7
Source dataset
uspto-grants-1995_08
Patent number
US05444055

Reaction notes

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