Triethylamine → 3beta-Tribenzylsilyloxy-7beta-hydroxy-15beta,16beta-methylene-5-androsten-17-one

HRID 1649463Notes

Reaction equation

HRID 1649463 reaction equation
[OH:1][C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C:4](=[CH:5][C@H:6]([OH:23])[C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]3[C@@H:9]3[CH2:22][C@@H:10]3[C:11]2=[O:21])[CH2:3]1.C(N(CC)CC)C.[CH2:31]([Si:38](Cl)([CH2:46][C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[CH2:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>C(Cl)Cl.CN(C1C=CC=CN=1)C>[CH2:46]([Si:38]([CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)([CH2:39][C:40]1[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1)[O:1][C@H:2]1[CH2:19][CH2:18][C@@:17]2([CH3:20])[C:4](=[CH:5][C@H:6]([OH:23])[C@@H:7]3[C@@H:16]2[CH2:15][CH2:14][C@@:12]2([CH3:13])[C@H:8]3[C@@H:9]3[CH2:22][C@@H:10]3[C:11]2=[O:21])[CH2:3]1)[C:47]1[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 87774Benzene, 1,1',1''-[(chlorosilylidyne)tris(methylene)]tris-HCID 445202043beta,7beta-Dihydroxy-15beta,16beta-methylene-5-androsten-17-one

Product 1

HCID 704669683beta-Tribenzylsilyloxy-7beta-hydroxy-15beta,16beta-methylene-5-androsten-17-oneYield 89.8%

Reagents, catalysts & solvents 2

HCID 218852-DimethylaminopyridineCatalystHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-20 °C

Procedure

A solution of 15.7 g of 3β,7β-dihydroxy-15β,16β-methylene-5-androsten-17-one in 750 ml of methylene chloride is combined with 9 ml of triethylamine and 200 mg of dimethylaminopyridine and cooled to -20° C. Within 30 minutes, 19.4 g of tribenzylsilyl chloride in 10 ml of methylene chloride is added dropwise thereto. The reaction mixture is stirred for one hour at -20° C. and one hour at 0° C., diluted with methylene chloride, and washed with 1 N hydrochloric acid, saturated sodium bicarbonate solution, and water. After drying over sodium sulfate, the mixture is concentrated under vacuum. Chromatography on silica gel with hexane-acetone yields 27.5 g of 3β-tribenzylsilyloxy-7β-hydroxy-15β,16β-methylene-5-androsten-17-one.

Workup

  1. washwashed with 1 N hydrochloric acid, saturated sodium bicarbonate solution, and water
  2. dry with materialAfter drying over sodium sulfate
  3. concentrationthe mixture is concentrated under vacuum

Sources & evidence

ORD record
ord-5a08b57ddc994faea0bacc130684fc52
Source dataset
uspto-grants-1983_11
Patent number
US04416985

Reaction notes

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