Hexachloroacetone → 11beta-Chloro-7alpha-methyl-estr-4-ene-3,17-dione

HRID 900681Notes

Reaction equation

HRID 900681 reaction equation
O[C@@H]1C[C@@]2(C)[C@@H:13]([CH2:14][CH2:15][C:16]2=[O:20])[C@H:12]2[C@H:3]1[C@@H:4]1[C:9]([CH2:10][C@H:11]2[CH3:21])=[CH:8][C:7](=[O:22])[CH2:6][CH2:5]1.Cl[C:24](Cl)(Cl)[C:25]([C:27]([Cl:30])(Cl)Cl)=O.[C:33]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[Cl:30][C@H:27]1[CH2:25][C@@:24]2([CH3:33])[C@@H:13]([CH2:14][CH2:15][C:16]2=[O:20])[C@H:12]2[C@H:3]1[C@@H:4]1[C:9]([CH2:10][C@H:11]2[CH3:21])=[CH:8][C:7](=[O:22])[CH2:6][CH2:5]1

Participants

5

Reactant 3

HCID 8303HexachloroacetoneHCID 11776TriphenylphosphineHCID 1202027311alpha-Hydroxy-7alpha-methylestr-4-ene-3,17-dione

Product 1

HCID 1202027411beta-Chloro-7alpha-methyl-estr-4-ene-3,17-dione

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 800 mg of 11α-hydroxy-7α-methylestr-4-ene-3,17-dione (F) in 8 ml of dichloromethane was mixed at 0° C. with 1.21 ml of hexachloroacetone and 764 mg of triphenylphosphine and stirred at room temperature for 4 hours. Then, it was diluted with dichloromethane, washed neutral, dried on sodium sulfate, concentrated by evaporation in a vacuum and chromatographed on silica gel with hexane/ethyl acetate. 430 mg of pure 11β-chloro-7α-methyl-estr-4-ene-3,17-dione (F′) with a melting point of 215.1° C. was obtained ([α]D20=+182.7° (c=0.5% in chloroform)).

Workup

  1. washwashed neutral
  2. customdried on sodium sulfate
  3. concentrationconcentrated by evaporation in a vacuum
  4. customchromatographed on silica gel with hexane/ethyl acetate

Sources & evidence

ORD record
ord-6c6d2eb11c62452494bc3996a5c5d427
Source dataset
uspto-grants-2008_04
Patent number
US07361645B2

Reaction notes

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