Acetic Acid → HCID 67341625, compound

HRID 1673291Notes

Reaction equation

HRID 1673291 reaction equation
[C:1]1([CH2:7][CH2:8][C:9](=O)[CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:12]([CH2:14][C:15]([O:17][CH3:18])=[O:16])#[N:13].C(O)(=O)C.C([O-])(=O)C.[NH4+]>C1(C)C=CC=CC=1>[C:12]([C:14](=[C:9]([CH3:10])[CH2:8][CH2:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:15]([O:17][CH3:18])=[O:16])#[N:13]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7747Methyl cyanoacetateHCID 17355Benzyl acetoneHCID 517165Ammonium Acetate

Product 1

HCID 67341625HCID 67341625, compoundYield 87.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 4-phenyl-2-butanone (1 g), methyl cyanoacetate (0.77 g), acetic acid (0.29 mL), ammonium acetate (0.11 g) and toluene (10 mL) was heated for reflux overnight removing the generated water. The reaction mixture was poured into water, and the resulting mixture was extracted with diethyl ether. The extract was washed with water and brine, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1) to give methyl 2-cyano-3-methyl-5-phenyl-2-pentenate (1.35 g). To this material were added methanol (10 mL) and N,N-dimethylformamide dimethyl acetal (0.95 mL), and the mixture was heated for reflux overnight. The reaction mixture was concentrated under reduced pressure. To the residue were added acetic acid (8 mL) and a solution of 30% hydrobromic acid in acetic acid (5.9 g), and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into ice water, and the resulting mixture was extracted with diethyl ether. The extract was washed with water twice, a saturated aqueous sodium hydrogen carbonate solution twice, water and brine successively, and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=6/1) to give the title compound (1.7 g)

Workup

  1. temperaturewas heated
  2. temperaturefor reflux overnight
  3. customremoving the generated water
  4. additionThe reaction mixture was poured into water
  5. extractionthe resulting mixture was extracted with diethyl ether
  6. washThe extract was washed with water and brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe solvent was removed under reduced pressure
  9. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1)

Sources & evidence

ORD record
ord-948f504add8e4a5f9d1c99b7657a1bea
Source dataset
uspto-grants-2011_08
Patent number
US07998975B2

Reaction notes

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