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

HRID 1682930Notes

Reaction equation

HRID 1682930 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[Cl:11][C:12]1[CH:13]=[C:14]([CH2:19][C:20]#[N:21])[CH:15]=[CH:16][C:17]=1[Cl:18].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:19]([C:20]#[N:21])([C:14]1[CH:15]=[CH:16][C:17]([Cl:18])=[C:12]([Cl:11])[CH:13]=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 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Sodium bis-(trimethylsilyl)amide (7910 mL, 1M, 7910 mmol) was cooled to 0° C. A solution of 3,4-dichlorophenylacetonitrile (700 g, 3763 mmol) in THF (2.50 L) was added maintaining the temperature of the reaction mixture between 0° and 20° C. After 1 hour, the above solution is added by candula to a solution of ethyl bromoacetate (910 mL) in THF (1.40 L) cooled to 0° C. The addition is carried out at such a rate that the temperature of the reaction mixture does not rise above 20° C. After 15 minutes, the reaction was quenched by the addition of t-butyl methyl ether (7.0 L) and water (3.5 L). The organic layer was separated and was extracted with water, 5% NaHCO3, and brine. 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: mp=69°-71° C.

Workup

  1. temperaturemaintaining the temperature of the reaction mixture between 0° and 20° C
  2. additionThe addition
  3. customdoes not rise above 20° C
  4. waitAfter 15 minutes
  5. customthe reaction was quenched by the addition of t-butyl methyl ether (7.0 L) and water (3.5 L)
  6. customThe organic layer was separated
  7. extractionwas extracted with water, 5% NaHCO3, and brine
  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-0d2ebbe9fc1b4d358c1b566af1fea410
Source dataset
uspto-grants-1997_06
Patent number
US05635510

Reaction notes

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