HCID 22872549, compound → HCID 86750802, compound

HRID 1585514Notes

Reaction equation

HRID 1585514 reaction equation
Br[C@@H:2]1[C@@H:29]([OH:30])[C@@:28]2([CH3:31])[C@@H:13]([CH2:14][C@@H:15]3[O:20][C@@:19]4([O:26][CH2:25][C@H:23]([CH3:24])[CH2:22][CH:21]4[Br:27])[C@@H:17]([CH3:18])[C@@H:16]32)[C@H:12]2[C@H:3]1[C@:4]1([CH3:33])[C@@H:9]([CH2:10][CH2:11]2)[CH2:8][C@@H:7]([OH:32])[CH2:6][CH2:5]1.BrC1C[C@@H](C)CO[C@@]21[C@@H](C)[C@@H]1[C@]3(C)[C@@H](C[C@@H]1O2)[C@H]1[C@@H]([C@]2(C)[C@@H](CC1)C[C@@H](O)CC2)CC3=O>N1C=CC=CC=1.[Ag]=O>[Br:27][CH:21]1[CH2:22][C@@H:23]([CH3:24])[CH2:25][O:26][C@@:19]21[C@@H:17]([CH3:18])[C@@H:16]1[C@:28]3([CH3:31])[C@@H:13]([CH2:14][C@@H:15]1[O:20]2)[C@H:12]1[C@@H:3]([C@:4]2([CH3:33])[C@@H:9]([CH2:10][CH2:11]1)[CH2:8][C@@H:7]([OH:32])[CH2:6][CH2:5]2)[C@H:2]1[O:30][C@@H:29]31

Participants

5

Reactant 2

HCID 22872549HCID 22872549, compoundHCID 54041341HCID 54041341, compound

Product 1

HCID 86750802HCID 86750802, compound

Reagents, catalysts & solvents 2

HCID 92152Silver(II) oxideCatalystHCID 1049PyridineSolvent

Procedure

The following procedure is a variation of that described in Helv. Chim. Act., 1953, 36, 1241. (3β,5α,11α,12β,25R)-11,23-dibromospirostan-3,12-diol (18.08 g) was dissolved in pyridine (500 mL) at room temperature and treated with silver oxide (70.0 g). The resulting mixture was stirred in the dark for 71 hours. The mixture was filtered and the solid washed with ether and then chloroform. These washes were combined with the filtrate and concentrated. The resulting solid was purified by flash chromatography (1:1 hexane:ethyl acetate) to give 12.2 g of a 1:1 mixture of the title compound and (3β,5α,25R)-23-bromospirostan-3-ol-12-one. Further chromatography (7:3 hexane:ethyl acetate) provides pure title compound. (3β,5α,11β,12α,25R)-23-bromo-12-(trichloroacetoxy)spirostan-3,11 -diol: Using the procedure described in J. Chem. Soc., 1956, 4330, (3β,5α, 11β,12β,25R)-23-bromo-11,12-epoxyspirostan-3-ol was treated with trichloroacetic acid in toluene at room temperature for 3 days to give the title compound. (3β,5α, 11β,12α,25R)-23-bromo-spirostan-3,11,12-triol: Using the procedure described in J. Chem. Soc., 1956, 4330, (3β,5α,11β,12α,25R)-23-bromo-12-(trichloroacetoxy)spirostan-3,11-diol was saponified with sodium hydroxide in water and ethanol to give the title compound.

Workup

  1. filtrationThe mixture was filtered
  2. washthe solid washed with ether
  3. concentrationconcentrated
  4. customThe resulting solid was purified by flash chromatography (1:1 hexane:ethyl acetate)
  5. customto give

Sources & evidence

ORD record
ord-6c7d7c0fd37043198418bdebbcd288f3
Source dataset
uspto-grants-1999_08
Patent number
US05939398

Reaction notes

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