Acetic Anhydride → HCID 14284770, compound

HRID 1088191Notes

Reaction equation

HRID 1088191 reaction equation
[CH3:1][CH:2]([C@H:4](/[CH:6]=[CH:7]/[C@H:8]([C@@H:10]1[C@:27]2([CH3:28])[C@H:13]([C@H:14]3[C@H:24]([CH2:25][CH2:26]2)[C@:22]2([CH3:23])[C@H:17]([CH2:18][CH:19]=[CH:20][CH2:21]2)[C:16](=[O:29])[CH2:15]3)[CH2:12][CH2:11]1)[CH3:9])[CH3:5])[CH3:3].C[N+]1([O-])[CH2:36][CH2:35][O:34]CC1.S([O-])(O)=[O:39].[Na+].[C:43]([O:46]C(=O)C)(=[O:45])[CH3:44]>O1CCCC1.O.N1C=CC=CC=1.[Os](=O)(=O)(=O)=O>[C:43]([O:46][C@@H:20]1[CH2:21][C@@:22]2([CH3:23])[C@@H:17]([C:16](=[O:29])[CH2:15][C@@H:14]3[C@@H:24]2[CH2:25][CH2:26][C@@:27]2([CH3:28])[C@H:13]3[CH2:12][CH2:11][C@@H:10]2[C@H:8]([CH3:9])/[CH:7]=[CH:6]/[C@H:4]([CH3:5])[CH:2]([CH3:1])[CH3:3])[CH2:18][C@@H:19]1[O:39][C:35](=[O:34])[CH3:36])(=[O:45])[CH3:44]

Participants

9

Reactant 4

HCID 7918Acetic AnhydrideHCID 82029Methyl morpholine oxideHCID 11025694HCID 11025694, compoundHCID 23665763Sodium Bisulfite

Product 1

HCID 14284770HCID 14284770, compoundYield 12%

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent3×HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Procedure

(22E, 24R)-5α-Ergosta-2,22-dien-6-one (S. Takatsuto and N. Ikekawa, Chem. Pharm. Bull., 32, 2001 (1984)) (15.0 g, 37.9 mmol) was dissolved in a solvent mixture of tetrahydrofuran (100 ml) and water (10 ml), added with osmium tetraoxide (500 mg) and N-methyl-morpholine-N-oxide (15 g), and stirred at room temperature for 6 hours. Water (30 ml) and sodium hydrogen sulfite (1 g) were added thereto, and after stirring at room temperature for 30 minutes, extracted with dichloromethane. The obtained organic layer was washed with 2N hydrochloric acid and then with water, and dried over anhydrous magnesium sulfate. A product obtained by removal of solvents with an evaporator was dissolved in pyridine (100 ml), 50 ml of acetic anhydride was added thereto, and stirred at 60° C. overnight. After cooling, 100 ml of water was added thereto and left still for 30 minutes, then extracted with ethyl acetate. The obtained organic layer was washed with 2N hydrochloric acid, with saturated aqueous solution of sodium hydrogencarbonate and with saturated brine, successively, and dried over anhydrous magnesium sulfate, then solvents were removed by an evaporator to give a crude product. It was purified by means of silica-gel column chromatography to give (22E, 24R)-2α,3α-diacetoxy-5α-ergost-22-en-6-one (2.0 g, 12 %):

Workup

  1. stirringafter stirring at room temperature for 30 minutes
  2. extractionextracted with dichloromethane
  3. washThe obtained organic layer was washed with 2N hydrochloric acid
  4. dry with materialwith water, and dried over anhydrous magnesium sulfate
  5. customA product obtained by removal of solvents with an evaporator
  6. stirringstirred at 60° C. overnight
  7. temperatureAfter cooling
  8. waitleft still for 30 minutes
  9. extractionextracted with ethyl acetate
  10. washThe obtained organic layer was washed with 2N hydrochloric acid, with saturated aqueous solution of sodium hydrogencarbonate and with saturated brine
  11. dry with materialsuccessively, and dried over anhydrous magnesium sulfate
  12. customsolvents were removed by an evaporator
  13. customto give a crude product
  14. customIt was purified by means of silica-gel column chromatography

Sources & evidence

ORD record
ord-38543f6bddfc44ef88ebfbe66d8e8de4
Source dataset
uspto-grants-1990_10
Patent number
US04961775

Reaction notes

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