Water → HCID 15463288, compound

HRID 2270541Notes

Reaction equation

HRID 2270541 reaction equation
C=[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)[C:9](=O)[CH2:8]3)[CH2:5][CH2:4]1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.[Na].O>O1CCOCC1.C(OC)(C)(C)C>[CH2:2]=[C:3]1[CH2:4][CH2:5][C@H:6]2[C@H:7]3[C@H:17]([CH2:18][CH2:19][C@:20]12[CH3:21])[C@:15]1([CH3:16])[C:10](=[CH:11][C:12](=[O:22])[CH:13]=[CH:14]1)[CH2:9][CH2:8]3

Participants

7

Reactant 4

HCID 962WaterHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 5360545SodiumHCID 15429665Pregna-4,20-dien-3,6-dione

Product 1

HCID 15463288HCID 15463288, compoundYield 50.3%

Reagents, catalysts & solvents 2

HCID 15413tert-Butyl methyl etherSolventHCID 312751,4-DioxaneSolvent

Procedure

Refer to FIG. 190. A solution of 17-methylenandrost-4-en-3-one (9, 1.0001 g, 3.5160 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 2.43 g, 10.7 mmol) in dioxane (60 ml, freshly distilled after overnight reflux over sodium) was refluxed 6 h and then cooled with swirling in tap water. Methyl t-butyl ether (MTBE, 50 ml) was added and the suspension was filtered through diatomaceous earth. The residue was washed with two 50 ml portions of MTBE and the combined filtrates were concentrated under reduced pressure. Flash chromatography of the residue (20% ethyl acetate/hexanes on silica gel) followed by recrystallization from 95% ethanol gave off-white crystals (498.9 mg, 1.767 mmol, 50%), m.p. 155-157° C.

Workup

  1. temperaturewas refluxed 6 h
  2. temperaturecooled
  3. filtrationthe suspension was filtered through diatomaceous earth
  4. washThe residue was washed with two 50 ml portions of MTBE
  5. concentrationthe combined filtrates were concentrated under reduced pressure
  6. customFlash chromatography of the residue (20% ethyl acetate/hexanes on silica gel) followed by recrystallization from 95% ethanol

Sources & evidence

ORD record
ord-7648fd2d66f44d4a8890cac62f2d52f9
Source dataset
uspto-grants-2001_12
Patent number
US06331534B1

Reaction notes

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