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

HRID 1604283Notes

Reaction equation

HRID 1604283 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-oneYield 22.1%

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 5i (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, 22%).

Workup

  1. washwashed with two 100 mL portions of 5i (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)

Sources & evidence

ORD record
ord-9d5bf60da2bb4c4d9c7f0fbe59ac3181
Source dataset
uspto-grants-1999_11
Patent number
US05994333

Reaction notes

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