Ethyl cyanoacetate → HCID 66924744, compound

HRID 554175Notes

Reaction equation

HRID 554175 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:10])[CH3:9].BrBr.[C:13]([CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])#[N:14].C(=O)([O-])[O-].[K+].[K+]>C(OCC)C.CC(C)=O.O>[C:13]([CH:15]([CH2:9][C:8]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[CH3:1])=[O:10])[C:16]([O:18][CH2:19][CH3:20])=[O:17])#[N:14]

Participants

8

Reactant 4

HCID 7764Ethyl cyanoacetateHCID 113402-MethylacetophenoneHCID 11430Potassium CarbonateHCID 24408Bromine

Product 1

HCID 66924744HCID 66924744, compoundYield 189.3%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
25 °C

Procedure

2′-Methylacetophenone (13.42 g) was dissolved in diethyl ether (100 mL), and bromine (16.0 g) 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 30 min. Water was added to the reaction mixture and the mixture was extracted with diethyl ether. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give crude 1-bromo-1-(2-methylphenyl)ethanone (21.3 g) as an oil. To ethyl cyanoacetate (79.20 g) was added potassium carbonate (27.64 g), and the mixture was stirred at 43-45° C. for 45 min. A solution (150 mL) of crude 1-bromo-1-(2-methylphenyl)ethanone (21.3 g) in acetone was added dropwise over 30 min. After completion of the dropwise addition, the mixture was stirred at room temperature for 16 hr. The reaction mixture was filtrated, 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=10:1→8:1) to give the title compound as a pale-yellow oil (yield 46.44 g, about 100%).

Workup

  1. additionAfter dropwise addition
  2. extractionthe mixture was extracted with diethyl ether
  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-(2-methylphenyl)ethanone (21.3 g) as an oil
  7. stirringthe mixture was stirred at 43-45° C. for 45 min
  8. additionAfter completion of the dropwise addition
  9. stirringthe mixture was stirred at room temperature for 16 hr
  10. filtrationThe reaction mixture was filtrated
  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=10:1→8:1)

Sources & evidence

ORD record
ord-c16c4fa96996423ab25846da1b43875f
Source dataset
uspto-grants-2011_11
Patent number
US08048909B2

Reaction notes

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