m-Chloroperbenzoic acid → HCID 67924634, compound

HRID 1087307Notes

Reaction equation

HRID 1087307 reaction equation
[C:1]([O: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:16]4[C@:28]([CH3:36])([CH2:29][CH2:30][C:31]=32)[C@@H:19]([C@H:20]([CH3:27])[CH2:21][CH2:22][CH2:23][CH:24]([CH3:26])[CH3:25])[CH2:18][CH:17]=4)[C:11]1([CH3:38])[CH3:37])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClC1C=CC=C(C(OO)=[O:47])C=1>C(OCC)C.C(=O)(O)[O-].[Na+]>[C:1]([O: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:16]4[C@:28]([CH3:36])([CH2:29][CH2:30][C:31]=32)[C@@H:19]([C@H:20]([CH3:27])[CH2:21][CH2:22][CH2:23][CH:24]([CH3:26])[CH3:25])[CH2:18][C:17]4=[O:47])[C:11]1([CH3:38])[CH3:37])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 10029545HCID 10029545, compound

Product 1

HCID 67924634HCID 67924634, compoundYield 75.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a solution of 3β-benzoyloxy-4,4-dimethyl-5α-cholest-8,14-diene (5.0 g, 10.2 mmol) in diethyl ether solution (300 mL) and 0.5M aqueous sodium bicarbonate (300 mL) was added meta-chloro-perbenzoic acid (2.44 g, 11.3 mmol) (Aldrich). After 30 min, the ether fraction was separated from the sodium bicarbonate layer and the aqueous fraction was repeatedly extracted with diethyl ether (5×500 mL). The organic fractions were combined, washed with brine (1×100 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo to about 150 ml. This ether solution of 38a was promptly cooled (0°) and treated dropwise with boron trifluoride etherate (26 mL, 22.5 mmol (Aldrich). After 30 min, the reaction was quenched with ice water (200 mL) and the aqueous phase was reextracted with ether (3×100 mL). The combined ether fractions were extracted with saturated sodium bicarbonate solution (1×200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The residue was crystallized from isopropanol (75 mL) to afford 4.10 g of 3β-benzoyloxy-4,4-dimethyl-5β-cholest-8-en-15-one (Compound 40a) in 75% yield.

Workup

  1. customthe ether fraction was separated from the sodium bicarbonate layer
  2. extractionthe aqueous fraction was repeatedly extracted with diethyl ether (5×500 mL)
  3. washwashed with brine (1×100 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo to about 150 ml
  7. temperatureThis ether solution of 38a was promptly cooled (0°)
  8. additiontreated dropwise with boron trifluoride etherate (26 mL, 22.5 mmol (Aldrich)
  9. waitAfter 30 min
  10. customthe reaction was quenched with ice water (200 mL)
  11. extractionThe combined ether fractions were extracted with saturated sodium bicarbonate solution (1×200 mL)
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo
  15. customThe residue was crystallized from isopropanol (75 mL)

Sources & evidence

ORD record
ord-77481b08311a49bda503600be54bd4fa
Source dataset
uspto-grants-1991_07
Patent number
US05034548

Reaction notes

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