2-Methyl-2-pentenal → Diisopropylether hexane

HRID 1184994Notes

Reaction equation

HRID 1184994 reaction equation
[Mg].Br[C:3]1[CH:4]=[C:5]([O:9]C)[CH:6]=[CH:7][CH:8]=1.CC(=[CH:15][CH2:16][CH3:17])C=O>BrC1C=C(OC)C=CC=1.C1COCC1.[Cu]I>[CH:5]([O:9][CH:16]([CH3:15])[CH3:17])([CH3:6])[CH3:4].[CH3:5][CH2:4][CH2:3][CH2:8][CH2:7][CH3:6]

Participants

7

Reactant 3

HCID 121772-Methyl-2-pentenalHCID 169713-BromoanisoleHCID 5462224Magnesium

Product 1

HCID 21881879Diisopropylether hexane

Reagents, catalysts & solvents 3

HCID 169713-BromoanisoleCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-70 °C

Procedure

To 1.46 g (0.06 mol) of magnesium were added 50 mL of dry THF. 5 drops of 3-bromoanisole were added to this mixture and the resulting suspension was refluxed until the reaction started. Then, a solution of 7.63 mL of 3-bromoanisole (0.06 mol) in 15 mL of dry THF was slowly added dropwise, thereby maintaining a constant reflux of the reaction mixture. After addition and refluxing of the reaction mixture for another hour, the mixture was cooled to −70° C. At this temperature 11.4 g (0.06 mol) copper(I) iodide (CuI) and 30 mL of dry THF were added. The mixture was then allowed to warm to around −65 to −60° C. At this temperature, commercially available 2-methyl-2-pentenal, dissolved in 15 mL of dry THF were added slowly to the reaction mixture. After stirring for 1 h at −65-−60° C., the reaction mixture was allowed to warm to 0° C. The reaction mixture was hydrolyzed by addition of 50 mL of a saturated aqueous solution of NH4HSO4. The mixture was then extracted three times with 100 mL of diethyl ether. The combined organic layers were dried over MgSO4. The organic solvent was evaporated and the remaining residue was dried in vacuo. CC (eluent: diisopropyl ether/n-hexane (1:30)) yielded 2.3 g (29%) of B2 as a colorless oil.

Workup

  1. temperaturethe resulting suspension was refluxed until the reaction
  2. temperaturemaintaining
  3. temperaturea constant reflux of the reaction mixture
  4. additionAfter addition
  5. temperaturerefluxing of the reaction mixture for another hour
  6. temperatureto warm to around −65 to −60° C
  7. additionwere added slowly to the reaction mixture
  8. temperatureto warm to 0° C
  9. extractionThe mixture was then extracted three times with 100 mL of diethyl ether
  10. dry with materialThe combined organic layers were dried over MgSO4
  11. customThe organic solvent was evaporated
  12. customthe remaining residue was dried in vacuo

Sources & evidence

ORD record
ord-10103a82f11e49a393c9ecdf2617ee39
Source dataset
uspto-grants-2014_03
Patent number
US08669399B2

Reaction notes

Loading…