Ethanol → Colestolone

HRID 2293937Notes

Reaction equation

HRID 2293937 reaction equation
C([O:9][C@H:10]1[CH2:34][CH2:33][C@@:32]2([CH3:35])[C@@H:12]([CH2:13][CH:14]=[C:15]3[C@@H:31]2[CH2:30][CH2:29][C@@:28]2([CH3:36])[C@@:16]43[O:37][C@H:17]4[CH2:18][C@@H:19]2[C@H:20]([CH3:27])[CH2:21][CH2:22][CH2:23][CH:24]([CH3:26])[CH3:25])[CH2:11]1)(=O)C1C=CC=CC=1.C(O)C.S(=O)(=O)(O)O>O>[OH:9][C@H:10]1[CH2:34][CH2:33][C@@:32]2([CH3:35])[C@@H:12]([CH2:13][CH2:14][C:15]3[C@@H:31]2[CH2:30][CH2:29][C@@:28]2([CH3:36])[C:16]=3[C:17](=[O:37])[CH2:18][C@@H:19]2[C@H:20]([CH3:27])[CH2:21][CH2:22][CH2:23][CH:24]([CH3:26])[CH3:25])[CH2:11]1

Participants

5

Reactant 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 14696446HCID 14696446, compound

Product 1

HCID 10046567ColestoloneYield 146.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

A mixture of 3β-benzoyloxy-14α,15α-epoxy-5α-cholest-7-ene (26, 12.0 g, 23.8 mmol), 95% ethanol (300 mL), and water (35 mL) was cooled to 5° C. in an ice water bath. To this solution was added, in portions of 5 mL, concentrated sulfuric acid (65.0 mL). After the addition (~5 min) the reaction mixture was heated under reflux for 22 h. Stirring must be effective to prevent clumping of the starting material. The clear reaction mixture was cooled to ambient temperature, then poured into ice (700 g). A sticky precipitate was formed (could not be filtered). The water phase was extracted three times with ethyl acetate (400, 200, and 200 mL). The combined ethyl acetate phase was washed with water, 5% sodium bicarbonate, and sodium chloride solution, and dried over sodium sulfate. Evaporation of the solvent gave a semisolid yellowish compound (14 g). The crude compound 27 was purified by flash chromatography (4.0×35 cm column) and eluted with ethyl acetate/hexane (1:3). Fractions containing product were combined and evaporated to give after crystallization from methanol/water pure product as fine needles 4.5 (47%). Mp, NMR, and IR data were in agreement with published data.

Workup

  1. additionAfter the addition (~5 min) the reaction mixture
  2. temperaturewas heated
  3. temperatureunder reflux for 22 h
  4. temperatureThe clear reaction mixture was cooled to ambient temperature
  5. customA sticky precipitate was formed (could not
  6. filtrationbe filtered)
  7. extractionThe water phase was extracted three times with ethyl acetate (400, 200, and 200 mL)
  8. washThe combined ethyl acetate phase was washed with water, 5% sodium bicarbonate, and sodium chloride solution
  9. dry with materialdried over sodium sulfate
  10. customEvaporation of the solvent

Sources & evidence

ORD record
ord-37143db2398941988cc9294cedf8b886
Source dataset
uspto-grants-1997_11
Patent number
US05688780

Reaction notes

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