Dimethylcarbamoyl Chloride → tert-Butyl (E)-3-(2-cyano-4-pyridyl)acrylate

HRID 499596Notes

Reaction equation

HRID 499596 reaction equation
[N:1]1[CH:6]=[CH:5][C:4](/[CH:7]=[CH:8]/[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[CH:3][CH:2]=1.ClC1C=CC=C(C(OO)=O)C=1.C[Si]([C:31]#[N:32])(C)C.CN(C)C(Cl)=O>C(OCC)(=O)C.O>[C:31]([C:2]1[CH:3]=[C:4](/[CH:7]=[CH:8]/[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH:5]=[CH:6][N:1]=1)#[N:32]

Participants

7

Reactant 4

HCID 6598Dimethylcarbamoyl ChlorideHCID 70297m-Chloroperbenzoic acidHCID 82115Trimethylsilyl cyanideHCID 11805847tert-Butyl (E)-3-(4-Pyridyl)acrylate

Product 1

HCID 59750116tert-Butyl (E)-3-(2-cyano-4-pyridyl)acrylateYield 99%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

tert-Butyl (E)-3-(4-pyridyl)acrylate (0.88 g, 4.3 mmol) was dissolved in ethyl acetate (4 ml), and 3-chloroperbenzoic acid (ca. 77%, 0.95 g, 4.3 mmol) was added thereto. The reaction mixture was stirred at room temperature for 45 hrs and subjected to a silica gel (40 g) column chromatography. The fractions eluted with ethyl acetate-ethanol (4:1) were collected and concentrated. The residue was dissolved in nitroethane (5 ml), and trimethylsilyl cyanide (0.63 g, 6.3 mmol) and N,N-dimethylcarbamoyl chloride (0.68 g, 6.3 mmol) were added thereto. The reaction mixture was stirred at room temperature for 20 hrs and combined with ethyl acetate and water. The organic layer was successively washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was subjected to silica gel (30 g) column chromatography. The fractions eluted with hexane-ethyl acetate (5:1, v/v) were collected and concentrated to give the titled compound (0.73 g, 99%).

Workup

  1. washThe fractions eluted with ethyl acetate-ethanol (4:1)
  2. customwere collected
  3. concentrationconcentrated
  4. dissolutionThe residue was dissolved in nitroethane (5 ml)
  5. stirringThe reaction mixture was stirred at room temperature for 20 hrs
  6. washThe organic layer was successively washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe solvent was evaporated
  9. washThe fractions eluted with hexane-ethyl acetate (5:1
  10. customv/v) were collected
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-351ccb9af16b4883846c827f15dfe60b
Source dataset
uspto-grants-2010_08
Patent number
US07767665B2

Reaction notes

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