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

HRID 1080630Notes

Reaction equation

HRID 1080630 reaction equation
Cl.[NH2:2][OH:3].[OH:4][C@H:5]1[CH2:25][CH2:24][C@@:23]2([CH3:26])[C@H:7]([CH2:8][CH2:9][C@@H:10]3[C@@H:22]2[CH2:21][CH2:20][C@@:19]2([CH3:27])[C@:11]3([OH:28])[CH2:12][CH2:13][C@@H:14]2/[CH:15]=[CH:16]/[CH:17]=O)[CH2:6]1>[OH-].[Na+].O1CCOCC1.O>[OH:3]/[N:2]=[CH:17]/[CH:16]=[CH:15]/[C@H:14]1[CH2:13][CH2:12][C@:11]2([OH:28])[C@H:10]3[C@H:22]([CH2:21][CH2:20][C@:19]12[CH3:27])[C@:23]1([CH3:26])[C@@H:7]([CH2:6][C@@H:5]([OH:4])[CH2:25][CH2:24]1)[CH2:8][CH2:9]3

Participants

6

Reactant 2

HCID 443297Hydroxyamine hydrochlorideHCID 10736377(E)-3beta,14beta-dihydroxy-5beta-pregn-20-ene-21-carboxaldehyde

Product 1

HCID 15292636(3S,5R,8R,9S,10S,13R,14S,17R)-17-[(E,3E)-3-hydroxyiminoprop-1-enyl]-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,14-diolYield 63.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 14798Sodium HydroxideSolventHCID 312751,4-DioxaneSolvent2×

Procedure

To a solution of 0.65 g of hydroxylamine hydrochloride in 41 ml of 1N NaOH and 30 ml of dioxane a solution of 2.70 g of (E)-3β,14β-dihydroxy-5β-pregn-20-ene-21-carboxaldehyde (Fullerton D. S. et al., J. Med. Chem., 1976, 19,1330) in 40 ml of dioxane was added dropwise at room temperature. After 20 hrs the solution was diluted with water and extracted with methylene chloride. The crude product was purified by flash chromatography (SiO2) using hexane/ethyl acetate 1/1 as the eluant. The fractions containing the title compound were collected and evaporated to dryness. The residue was ground with di-iso-propyl ether to give 1.80 g of the title compound (I-am), as a white solid.

Workup

  1. extractionextracted with methylene chloride
  2. customThe crude product was purified by flash chromatography (SiO2)
  3. additionThe fractions containing the title compound
  4. customwere collected
  5. customevaporated to dryness

Sources & evidence

ORD record
ord-f70df69aa74841fb821eb5e518dceaa7
Source dataset
uspto-grants-1996_12
Patent number
US05583127

Reaction notes

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