Ammonium Chloride → Methyl 2-acetyl-3-methyl-3-phenylbutanoate

HRID 45219Notes

Reaction equation

HRID 45219 reaction equation
[C:1]1([Mg]Br)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:9]([C:12](=[C:17]([CH3:19])[CH3:18])[C:13]([O:15][CH3:16])=[O:14])(=[O:11])[CH3:10].[NH4+].[Cl-]>CCOCC.[Cu]I>[C:9]([CH:12]([C:17]([CH3:19])([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[CH3:18])[C:13]([O:15][CH3:16])=[O:14])(=[O:11])[CH3:10]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 12576903Methyl 2-acetyl-3-methylbut-2-enoateHCID 178418255HCID 178418255, compound

Product 1

HCID 86659735Methyl 2-acetyl-3-methyl-3-phenylbutanoateYield 67%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
0 °C

Procedure

To a suspension of 146 mg (0.8 mmol) of anhydrous CuI (I) in 5 mL of anhydrous ether are added, at 0° C., under a stream of argon, 3.6 mL (10.9 mmol) of a 3M solution of phenyl magnesium bromide in Et2O. After stirring for 30 minutes at 0° C., 1 g (6.4 mmol) of methyl 2-acetyl-3-methylbut-2-enoate is added in a single portion. The mixture is allowed to warm to room temperature and stirring is continued for 18 hours. The reaction mixture is then treated with 100 mL of saturated NH4Cl solution, the phases are separated by settling, and the organic phase is again treated with 100 mL of saturated NH4Cl solution. The aqueous phases are extracted with 4×100 mL of DCM. The organic phases are combined, dried over anhydrous Na2SO4 and concentrated under reduced pressure. After purification by chromatography on silica gel, eluting with a 95/5 cyclohexane/EtOAc mixture, 1 g of methyl 2-acetyl-3-methyl-3-phenylbutanoate is obtained in the form of a colourless oil.

Workup

  1. temperatureto warm to room temperature
  2. stirringstirring
  3. waitis continued for 18 hours
  4. customthe phases are separated
  5. additionthe organic phase is again treated with 100 mL of saturated NH4Cl solution
  6. extractionThe aqueous phases are extracted with 4×100 mL of DCM
  7. dry with materialdried over anhydrous Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customAfter purification by chromatography on silica gel
  10. washeluting with a 95/5 cyclohexane/EtOAc mixture

Sources & evidence

ORD record
ord-d66cab7cd1934da19ba332f267c9a582
Source dataset
uspto-grants-2013_09
Patent number
US08541455B2

Reaction notes

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