Ammonium Chloride → 1alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17beta-{4-ethyl-4-(triethylsilyloxy)hexyloxymethyl}androst-5-ene

HRID 1792228Notes

Reaction equation

HRID 1792228 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH2:15][C@@H:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH2:19][C@@H:20]2[CH2:28][OH:29])[CH2:12][C@@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[K+].C1OCCOCCOCCOCCOCCOC1.Br[CH2:59][CH2:60][CH2:61][C:62]([CH2:73][CH3:74])([O:65][Si:66]([CH2:71][CH3:72])([CH2:69][CH3:70])[CH2:67][CH3:68])[CH2:63][CH3:64].[Cl-].[NH4+]>O1CCCC1>[Si:1]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH2:15][C@@H:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH2:19][C@@H:20]2[CH2:28][O:29][CH2:59][CH2:60][CH2:61][C:62]([CH2:73][CH3:74])([O:65][Si:66]([CH2:71][CH3:72])([CH2:67][CH3:68])[CH2:69][CH3:70])[CH2:63][CH3:64])[CH2:12][C@@H:11]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:32])[CH3:33])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 5

HCID 25517Ammonium ChlorideHCID 2855718-Crown-6HCID 82127Potassium hydrideHCID 220276701-Bromo-4-ethyl-4-(triethylsilyloxy)hexaneHCID 696299821alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17beta-(hydroxymethyl)androst-5-ene

Product 1

HCID 696301241alpha,3beta-Bis(tert-butyldimethylsilyloxy)-17beta-{4-ethyl-4-(triethylsilyloxy)hexyloxymethyl}androst-5-eneYield 99.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

1α,3β-Bis(tert-butyldimethylsilyloxy)-17β-(hydroxymethyl)androst-5-ene (11.0 g) was dissolved in tetrahydrofuran. Under cooling with ice, potassium hydride (30% in oil, 200.3 g) and 18-crown-6 (2.64 g) were added to the solution, which was then stirred for 5 min. 1-Bromo-4-ethyl-4-(triethylsilyloxy)hexane (25.91 g) was then added to the mixture and reacted for 3.5 hours. After stopping the reaction by adding a saturated aqueous ammonium chloride solution, the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated under reduced pressure to remove the solvent. The resulting residue was purified by column chromatography (hexane:ethyl acetate=50:1) to give the titled compound (15.8 g).

Workup

  1. additionwere added to the solution, which
  2. customreacted for 3.5 hours
  3. customthe reaction
  4. extractionthe mixture was extracted with ethyl acetate
  5. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customthe filtrate was evaporated under reduced pressure
  8. customto remove the solvent
  9. customThe resulting residue was purified by column chromatography (hexane:ethyl acetate=50:1)

Sources & evidence

ORD record
ord-851c9b370e384106b3146c8a63abe960
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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