Carbon Tetrachloride → 7alpha-Chloro-5,6beta-epoxy-15beta,16beta-methylen-3beta-pivaloyloxy-5beta-androstan-17-one

HRID 65411Notes

Reaction equation

HRID 65411 reaction equation
[O:1]1[C@@H:3]2[C@H:4](O)[C@@H:5]3[C@@H:14]([C@@:15]4([CH3:27])[CH2:16][CH2:17][C@H:18]([O:20][C:21](=[O:26])[C:22]([CH3:25])([CH3:24])[CH3:23])[CH2:19][C@@:2]124)[CH2:13][CH2:12][C@@:10]1([CH3:11])[C@H:6]3[C@@H:7]2[CH2:29][C@@H:8]2[C:9]1=[O:28].[Cl:31]CCl.ClC(Cl)(Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>N1C=CC=CC=1>[Cl:31][C@@H:4]1[C@H:3]2[O:1][C@:2]32[C@:15]([CH3:27])([CH2:16][CH2:17][C@H:18]([O:20][C:21](=[O:26])[C:22]([CH3:25])([CH3:24])[CH3:23])[CH2:19]3)[C@@H:14]2[C@@H:5]1[C@H:6]1[C@@:10]([CH2:12][CH2:13]2)([CH3:11])[C:9](=[O:28])[C@H:8]2[CH2:29][C@@H:7]12

Participants

6

Reactant 4

HCID 5943Carbon TetrachlorideHCID 6344DichloromethaneHCID 11776TriphenylphosphineHCID 130759585,6beta-Epoxy-7beta-hydroxy-15beta,16beta-methylen-3beta-pivaloyloxy-5beta-androstan-17-one

Product 1

HCID 130759607alpha-Chloro-5,6beta-epoxy-15beta,16beta-methylen-3beta-pivaloyloxy-5beta-androstan-17-one

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A solution of 169 g of 5,6β-epoxy-7β-hydroxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one in a mixture of respectively 340 ml of dichloromethane, tetrachloromethane, and pyridine is combined with 200 g of triphenylphosphine and stirred for 2 hours at room temperature. The reaction solution is washed with water, dried over sodium sulfate, and evaporated to dryness under vacuum. The residue is stirred up with 310 ml of ethanol and filtered. The filter cake is washed with 175 ml of ethanol and dried under vacuum, thus obtaining 139.2 g of 7α-chloro-5,6β-epoxy-15β,16β-methylene-3β-pivaloyloxy-5β-androstan-17-one. An analytical sample, recrystallized from acetone-hexane, has a melting point of 228° C. [α]D =-100° (chloroform).

Workup

  1. washThe reaction solution is washed with water
  2. dry with materialdried over sodium sulfate
  3. customevaporated to dryness under vacuum
  4. stirringThe residue is stirred up with 310 ml of ethanol
  5. filtrationfiltered
  6. washThe filter cake is washed with 175 ml of ethanol
  7. customdried under vacuum

Sources & evidence

ORD record
ord-516606992516484ba946ff4032f48a0b
Source dataset
uspto-grants-1986_09
Patent number
US04614616

Reaction notes

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