Dichloromethane → 3beta-(Tert.-butyldimethylsilyloxy)-7alpha-chloro-5,6beta-epoxy-15beta,16beta-methylene-5beta-androstan-17-one

HRID 65414Notes

Reaction equation

HRID 65414 reaction equation
[C:1]([Si:5]([CH3:31])([CH3:30])[O:6][C@H:7]1[CH2:24][CH2:23][C@@:22]2([CH3:25])[C@@:9]3([O:29][C@@H:10]3[C@H:11](O)[C@@H:12]3[C@@H:21]2[CH2:20][CH2:19][C@@:17]2([CH3:18])[C@H:13]3[C@@H:14]3[CH2:27][C@@H:15]3[C:16]2=[O:26])[CH2:8]1)([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Cl)[Cl:52]>C(Cl)(Cl)(Cl)Cl.N1C=CC=CC=1>[C:1]([Si:5]([CH3:31])([CH3:30])[O:6][C@H:7]1[CH2:24][CH2:23][C@@:22]2([CH3:25])[C@@:9]3([O:29][C@@H:10]3[C@@H:11]([Cl:52])[C@@H:12]3[C@@H:21]2[CH2:20][CH2:19][C@@:17]2([CH3:18])[C@H:13]3[C@@H:14]3[CH2:27][C@@H:15]3[C:16]2=[O:26])[CH2:8]1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 11776TriphenylphosphineHCID 130759623beta-(Tert.-butyldimethylsilyloxy)-5,6beta-epoxy-7beta-hydroxy-15beta,16beta-methylene-5beta-androstan-17-one

Product 1

HCID 130759643beta-(Tert.-butyldimethylsilyloxy)-7alpha-chloro-5,6beta-epoxy-15beta,16beta-methylene-5beta-androstan-17-one

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

126 g of 3β-(tert.-butyldimethylsilyloxy)-5,6β-epoxy-7β-hydroxy-15β,16β-methylene-5β-androstan-17-one is dissolved in a mixture of 600 ml of methylene chloride, 600 ml of carbon tetrachloride, and 300 ml of pyridine and stirred with 193.8 g of triphenylphosphine for 2.5 hours. The mixture is then washed with water, dried over sodium sulfate, and concentrated under vacuum. Chromatography on silica gel with hexane-acetone yields 117.4 g of 3β-(tert.-butyldimethylsilyloxy)-7α-chloro-5,6β-epoxy-15β,16β-methylene-5β-androstan-17-one, mp 155.5° C. [α]D =-87° (chloroform).

Workup

  1. washThe mixture is then washed with water
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-1338a2a8b7d4465a94c1fc263f3ee3bc
Source dataset
uspto-grants-1986_09
Patent number
US04614616

Reaction notes

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