Iodine → HCID 58661772, compound

HRID 1363996Notes

Reaction equation

HRID 1363996 reaction equation
[Mg].II.Cl[CH2:5][CH2:6][CH2:7][CH2:8][O:9][CH3:10].[Br:11][C:12]1[C:13](=O)[CH2:14][CH2:15][CH2:16][C:17]=1[O:18]CC>C1COCC1.C(Br)Br>[Br:11][C:12]1[C:17](=[O:18])[CH2:16][CH2:15][CH2:14][C:13]=1[CH2:5][CH2:6][CH2:7][CH2:8][O:9][CH3:10]

Participants

7

Reactant 4

HCID 807IodineHCID 873631-Chloro-4-methoxybutaneHCID 5462224MagnesiumHCID 113334562-Bromo-3-ethoxy-2-cyclohexen-1-one

Product 1

HCID 58661772HCID 58661772, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 3024DibromomethaneCatalystHCID 8028TetrahydrofuranSolvent4×

Procedure

To magnesium turnings (9.84 g, 405 mmol) in dry THF (42 mL) as a solvent were added a few crystals of iodine and a few drops of CH2Br2. A solution of 1-chloro-4-methoxybutane (46.8 g, 382 mmol) in dry THF (90 mL) was added dropwise at a rate sufficient to maintain gentle reflux. The reaction mixture was then refluxed for 1 hour and then cooled to room temperature. The resulting Grignard reagent was then added dropwise to a suspension of CeCl3 (94.2 g, 382 mmol) in dry THF (750 mL) at 0° C. After stirring at room temperature for 2 hours, a solution of 2-bromo-3-ethoxy-cyclohex-2-enone (1) (60 g, 274 mmol) in dry THF (300 mL) was added dropwise at 0° C. The reaction mixture was stirred an additional 2 hours at room temperature and then quenched by adding a saturated NH4Cl solution (1000 mL). The mixture was further acidified to approximately pH 1 by the addition. of a 5% HCl solution and stirring was continued for an additional 2 hours. The organic layer was separated, the aqueous layer extracted with Et2O and the combined organic layers were dried over anhydrous MgSO4. The solvent was removed in vacuo and the residue purified over silica (using a isooctane/EtOAc 7:3 mixture as an eluent) to afford 65.5 g (92% yield) of the desired product as a light-yellow oil which was characterized as follows:

Workup

  1. temperatureto maintain gentle reflux
  2. temperatureThe reaction mixture was then refluxed for 1 hour
  3. stirringThe reaction mixture was stirred an additional 2 hours at room temperature
  4. customquenched
  5. additionby adding a saturated NH4Cl solution (1000 mL)
  6. additionThe mixture was further acidified to approximately pH 1 by the addition
  7. stirringof a 5% HCl solution and stirring
  8. waitwas continued for an additional 2 hours
  9. customThe organic layer was separated
  10. extractionthe aqueous layer extracted with Et2O
  11. dry with materialthe combined organic layers were dried over anhydrous MgSO4
  12. customThe solvent was removed in vacuo
  13. customthe residue purified over silica (

Sources & evidence

ORD record
ord-a35b60b8af67457d9055fb7fa3871884
Source dataset
uspto-grants-2011_02
Patent number
US07888338B2

Reaction notes

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