Sodium hydride → HCID 67301237, compound

HRID 1014973Notes

Reaction equation

HRID 1014973 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@:28]2([CH3:29])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:27]2[CH2:26][CH2:25][C@@:24]2([CH3:30])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@@H:21]([OH:23])[CH3:22])[CH2:12][C@@H:11]([O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].C1OCCOCCOCCOCCOC1.Br[CH2:57][C:58]([O:60][C:61]([CH3:64])([CH3:63])[CH3:62])=[O:59]>O1CCCC1.C(OCC)(=O)C.O>[Si:1]([O:8][C@@H:9]1[C@@:28]2([CH3:29])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:27]2[CH2:26][CH2:25][C@@:24]2([CH3:30])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@@H:21]([O:23][CH2:57][C:58]([O:60][C:61]([CH3:64])([CH3:63])[CH3:62])=[O:59])[CH3:22])[CH2:12][C@@H:11]([O:31][Si:32]([C:35]([CH3:37])([CH3:36])[CH3:38])([CH3:33])[CH3:34])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 24758Sodium hydrideHCID 3633615-Crown-5HCID 79177tert-Butyl bromoacetateHCID 120200781alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(S)-hydroxypregna-5,7,16-triene

Product 1

HCID 67301237HCID 67301237, compoundYield 82.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
72 °C

Procedure

A solution of 1α,3β-bis(tert-butyldimethylsilyloxy)-20(S)-hydroxypregna-5,7,16-triene (55.5 mg, 0.0993 mmol), sodium hydride (95%, 15 mg, 0.594 mmol) and 15-crown-5 (15 mg, 0.0681 mmol) in tetrahydrofuran (1 ml) was stirred at an external temperature of 72° C. for 1 hour, to which t-butyl bromoacetate (0.05 ml, 0.336 mmol) was then added at room temperature and further stirred at an external temperature of 72° C. for 5 hours and 15 minutes. After the reaction mixture was diluted with ethyl acetate, water was added dropwise under ice cooling. After washing with saturated aqueous sodium chloride, the organic layer was dried over anhydrous magnesium sulfate. After evaporation under reduced pressure to remove the solvent, the resulting residue was purified by preparative thin layer chromatography (0.5 mm×1 plate, hexane:ethyl acetate=10:1, developed once) to give the titled compound (55.1 mg, 82%) as a colorless oil.

Workup

  1. additionwas then added at room temperature
  2. additionwas added dropwise under ice cooling
  3. washAfter washing with saturated aqueous sodium chloride
  4. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  5. customAfter evaporation under reduced pressure
  6. customto remove the solvent
  7. customthe resulting residue was purified by preparative thin layer chromatography (0.5 mm×1 plate, hexane

Sources & evidence

ORD record
ord-8506a89f95fe45639e323251b3c455a6
Source dataset
uspto-grants-2011_07
Patent number
US07985744B2

Reaction notes

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