4'-Methoxyacetophenone → HCID 66924844, compound

HRID 554176Notes

Reaction equation

HRID 554176 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=[O:11])[CH3:10])=[CH:5][CH:4]=1.BrBr.[C:14]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])#[N:15].C(=O)([O-])[O-].[K+].[K+]>C(Cl)(Cl)Cl.C(OCC)C.CC(C)=O.O>[C:14]([CH:16]([CH2:10][C:9]([C:6]1[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=1)=[O:11])[C:17]([O:19][CH2:20][CH3:21])=[O:18])#[N:15]

Participants

9

Reactant 4

HCID 74764'-MethoxyacetophenoneHCID 7764Ethyl cyanoacetateHCID 11430Potassium CarbonateHCID 24408Bromine

Product 1

HCID 66924844HCID 66924844, compoundYield 115.9%

Reagents, catalysts & solvents 4

HCID 180AcetoneSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6212ChloroformSolvent2×

Conditions

Temperature
25 °C

Procedure

4′-Methoxyacetophenone (15.0 g) was dissolved in chloroform (70 mL) and diethyl ether (50 mL), and a solution of bromine (16.0 g) in chloroform (20 mL) was added dropwise while maintaining the reaction temperature at not higher than 25° C. After dropwise addition, the mixture was stirred at room temperature for 2 hr. Water was added to the reaction mixture and the mixture was extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give crude 1-bromo-1-(4-methoxyphenyl)ethanone (yield 22.05 g) as crystals. To ethyl cyanoacetate (79.20 g) was added potassium carbonate (27.65 g), and the mixture was stirred at 45° C. for 1 hr. A solution (100 mL) of crude 1-bromo-1-(4-methoxyphenyl)ethanone (22.0 g) in acetone was added dropwise over 20 min. After completion of the dropwise addition, the mixture was stirred at room temperature for 18 hr. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Water was added to the residue, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. An excess ethyl cyanoacetate contained in the obtained oil was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=9:1→3:1) to give the title compound as an oil (yield 30.25 g, about 100%).

Workup

  1. additionAfter dropwise addition
  2. extractionthe mixture was extracted with chloroform
  3. washThe extract was washed with saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customto give crude 1-bromo-1-(4-methoxyphenyl)ethanone (yield 22.05 g) as crystals
  7. stirringthe mixture was stirred at 45° C. for 1 hr
  8. additionAfter completion of the dropwise addition
  9. stirringthe mixture was stirred at room temperature for 18 hr
  10. filtrationThe reaction mixture was filtered
  11. concentrationthe filtrate was concentrated under reduced pressure
  12. additionWater was added to the residue
  13. extractionthe mixture was extracted with ethyl acetate
  14. washThe extract was washed with saturated brine
  15. dry with materialdried over anhydrous magnesium sulfate
  16. concentrationconcentrated under reduced pressure
  17. customwas evaporated under reduced pressure
  18. customthe residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate=9:1→3:1)

Sources & evidence

ORD record
ord-7cb1862389e1445b8491e9cfb84e4245
Source dataset
uspto-grants-2011_11
Patent number
US08048909B2

Reaction notes

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