Chloranil → Estra-4,6-diene-3,17-dione

HRID 1281664Notes

Reaction equation

HRID 1281664 reaction equation
[CH3:1][C@:2]12[CH2:18][CH2:17][C@H:16]3[C@@H:7]([CH2:8][CH2:9][C:10]4[C@@H:15]3[CH2:14][CH2:13][C:12](=[O:19])[CH:11]=4)[C@@H:6]1[CH2:5][CH2:4][C:3]2=[O:20].C1(Cl)C(=O)C(Cl)=C(Cl)C(=O)C=1Cl.CCOC(C)=O.CCCCCC>C(O)C>[CH3:1][C@:2]12[CH2:18][CH2:17][C@H:16]3[C@@H:7]([CH:8]=[CH:9][C:10]4[C@@H:15]3[CH2:14][CH2:13][C:12](=[O:19])[CH:11]=4)[C@@H:6]1[CH2:5][CH2:4][C:3]2=[O:20]

Participants

5

Reactant 3

HCID 8371ChloranilHCID 92834(+)-Estr-4-ene-3,17-dioneHCID 21226206Ethyl acetate hexane

Product 1

HCID 128845Estra-4,6-diene-3,17-dioneYield 46.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of dione 53 (5.0 g, 18.36 mmol) and chloranil (5.4 g, 22 mmol) in dry ethanol (500 mL) was stirred at 60-65° C. for 2 h. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with dichloromethane. The solid was removed by filtration, and the filtrate was concentrated to give a brown gum. Chromatography (20% EtOAc/hexane) yielded crude dione 54 as a yellow solid (2.3 g, 46%): 1H NMR (300 MHz, CDCl3) δ 0.94 (s, 3, CH3), 5.78 (s, 1), 6.25 (m, 2).

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. customthe residue was triturated with dichloromethane
  3. customThe solid was removed by filtration
  4. concentrationthe filtrate was concentrated
  5. customto give a brown gum

Sources & evidence

ORD record
ord-aeac78fc4c16439a99687eb51c74ac0b
Source dataset
uspto-grants-2002_09
Patent number
US06455517B1

Reaction notes

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