Ethyl bromoacetate → Diethyl 3-cyano-3-(3,4-dichlorophenyl)pentanedioate

HRID 1682931Notes

Reaction equation

HRID 1682931 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][C:10]#[N:11])[CH:5]=[CH:6][C:7]=1[Cl:8].C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Br[CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]>C1COCC1>[CH2:27]([O:26][C:24](=[O:25])[CH2:23][C:9]([C:10]#[N:11])([C:4]1[CH:5]=[CH:6][C:7]([Cl:8])=[C:2]([Cl:1])[CH:3]=1)[CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH3:28]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 76690(3,4-Dichlorophenyl)acetonitrileHCID 2724254Sodium bis(trimethylsilyl)amide

Product 1

HCID 54083037Diethyl 3-cyano-3-(3,4-dichlorophenyl)pentanedioate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

3,4-Dichlorophenylacetonitrile (30.0 g, 0.161 mol) and THF (100 mL) were combined and cooled in a dry-ice/acetone bath. Sodium bis-(trimethylsilyl)amide (324 mL, 1.0M in THF, 0.324 mol, 2 eq.) was added dropwise. After the addition was complete, the mixture was allowed to warm to ambient temperature. After 4 h, the mixture was cooled in a dry-ice/acetone bath. Ethyl bromoacetate (36 mL, 0.325 mol) was added dropwise. After the addition was complete, the mixture was allowed to warm to ambient temperature. The reaction mixture was partitioned between diethyl ether and water. The organic layer was extracted with H2O (3×150 mL), 1N HCl (2×100 mL), 5% NaHCO3 (2×100 mL), and brine (1×150 mL). The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to obtain a residue. The residue was recrystallized from diethyl ether to give the title compound:

Workup

  1. temperaturecooled in a dry-ice/acetone bath
  2. additionAfter the addition
  3. temperaturethe mixture was cooled in a dry-ice/acetone bath
  4. additionAfter the addition
  5. temperatureto warm to ambient temperature
  6. customThe reaction mixture was partitioned between diethyl ether and water
  7. extractionThe organic layer was extracted with H2O (3×150 mL), 1N HCl (2×100 mL), 5% NaHCO3 (2×100 mL), and brine (1×150 mL)
  8. dry with materialThe organic layer was dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customto obtain a residue
  12. customThe residue was recrystallized from diethyl ether

Sources & evidence

ORD record
ord-69c350fbff974867a54f15aa3313717f
Source dataset
uspto-grants-1997_06
Patent number
US05635510

Reaction notes

Loading…