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

HRID 65410Notes

Reaction equation

HRID 65410 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 1N 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 1N 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-30c997fbf9964100be0c226eb2515415
Source dataset
uspto-grants-1986_09
Patent number
US04614616

Reaction notes

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