2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → Pregna-1,4,20-trien-3-one

HRID 1953477Notes

Reaction equation

HRID 1953477 reaction equation
[CH2:1]=[CH:2][C@@H:3]1[C@:20]2([CH3:21])[C@H:6]([C@H:7]3[C@H:17]([CH2:18][CH2:19]2)[C@:15]2([CH3:16])[C:10](=[CH:11][C:12](=[O:22])[CH2:13][CH2:14]2)[CH2:9][CH2:8]3)[CH2:5][CH2:4]1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1C=CC=CC=1.CCOCC>[CH2:1]=[CH:2][C@@H:3]1[C@:20]2([CH3:21])[C@H:6]([C@H:7]3[C@H:17]([CH2:18][CH2:19]2)[C@:15]2([CH3:16])[C:10](=[CH:11][C:12](=[O:22])[CH:13]=[CH:14]2)[CH2:9][CH2:8]3)[CH2:5][CH2:4]1

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 15429659Pregna-4,20-dien-3-one

Product 1

HCID 13034987Pregna-1,4,20-trien-3-one

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Procedure

Pregna-4,20-dien-3-one (1, 1.19 g. 3.99 mmol) was refluxed for 24 h with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 2.72 g, 12.1 mmol) in 40 ml of benzene under Argon. The cooled suspension was diluted with ether and washed with two 100 ml portions of 5% (w/w) sodium hydroxide, two 100 ml portions of water and once with 100 ml of brine. Ether (100 ml) was added to the resulting emulsion, which was dried over sodium sulfate and then filtered through a column of sodium sulfate (20 g). After washing the residue twice with 50 ml portions of ether the combined filtrates were concentrated under reduced pressure and then flash chromatographed (25% ethyl acetate/hexanes on silica gel) to give a slightly yellow crystalline solid (0.26 g, 0.88 mmol, 226).

Workup

  1. washwashed with two 100 ml portions of 5% (w/w) sodium hydroxide, two 100 ml portions of water and once with 100 ml of brine
  2. additionEther (100 ml) was added to the resulting emulsion, which
  3. dry with materialwas dried over sodium sulfate
  4. filtrationfiltered through a column of sodium sulfate (20 g)
  5. washAfter washing the residue twice with 50 ml portions of ether the combined filtrates
  6. concentrationwere concentrated under reduced pressure
  7. customflash chromatographed (25% ethyl acetate/hexanes on silica gel)
  8. customto give a slightly yellow crystalline solid (0.26 g, 0.88 mmol, 226)

Sources & evidence

ORD record
ord-1311a4cfc66041b8a2fd9a809fcc71cd
Source dataset
uspto-grants-2000_09
Patent number
US06117860

Reaction notes

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