1-Bromo-3-methylbutane → 2,2,6-Trimethylheptan-3-one

HRID 358929Notes

Reaction equation

HRID 358929 reaction equation
[C:1](Cl)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[CH2:8]([Mg]Br)[CH2:9][CH:10]([CH3:12])[CH3:11].[Mg].C(Br)CC(C)C>CCOCC.[Cu]I>[CH3:3][C:2]([CH3:5])([C:1](=[O:6])[CH2:8][CH2:9][CH:10]([CH3:12])[CH3:11])[CH3:4]

Participants

7

Reactant 4

HCID 78911-Bromo-3-methylbutaneHCID 62493Pivaloyl chlorideHCID 5462224MagnesiumHCID 178418529HCID 178418529, compound

Product 1

HCID 200655012,2,6-Trimethylheptan-3-one

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent2×

Procedure

To a stirred mixture of pivaloyl chloride (6.02 g, 0.05 m) and copper (I) iodide (0.10 g, 0.6 mm) in dry ether (50 mls) at -60° C. under nitrogen was added dropwise isoamyl magnesium bromide [prepared from magnesium turnings (1.8 g, 0.075 m) and isoamyl bromide (7.55 g, 0.05 m) in dry ether (70 mls]. The cooling bath was removed and the reaction mixture stirred for 16 hours then poured cautiously into ice-cold dilute hydrochloric acid and extracted with ether. The combined ethereal extracts were washed with saturated aqueous sodium hydrogen carbonate solution, brine, dried (anhydrous MgSO4) and evaporated. The residue was chromatographed on silica using gradient elution (dichloromethane (0-30%) in petrol) to give the ketone as a pale yellow oil.

Workup

  1. customThe cooling bath was removed
  2. additionthen poured cautiously into ice-cold dilute hydrochloric acid
  3. extractionextracted with ether
  4. washThe combined ethereal extracts were washed with saturated aqueous sodium hydrogen carbonate solution, brine
  5. dry with materialdried (anhydrous MgSO4)
  6. customevaporated
  7. customThe residue was chromatographed on silica using gradient elution (dichloromethane (0-30%) in petrol)

Sources & evidence

ORD record
ord-61f54d5fe4e848dba641db799bb2c6fb
Source dataset
uspto-grants-1991_03
Patent number
US04999043

Reaction notes

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