Sodium hydride → Ethyl 5-cyano-5-(3,4-dichlorophenyl)pentanoate

HRID 377800Notes

Reaction equation

HRID 377800 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:5]=[C:6]([CH2:11][C:12]#[N:13])[CH:7]=[CH:8][C:9]=1[Cl:10].Br[CH2:15][CH2:16][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19]>C1COCC1>[C:12]([CH:11]([C:6]1[CH:7]=[CH:8][C:9]([Cl:10])=[C:4]([Cl:3])[CH:5]=1)[CH2:15][CH2:16][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])#[N:13]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 76300Ethyl 4-bromobutyrateHCID 76690(3,4-Dichlorophenyl)acetonitrile

Product 1

HCID 22741808Ethyl 5-cyano-5-(3,4-dichlorophenyl)pentanoateYield 45.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

11.8 g of a 55% dispersion of sodium hydride in oil are suspended in 100 ml of THF and cooled in an ice bath, a solution of 50 g of 3,4-dichlorophenylacetonitrile in 50 ml of THF is added dropwise and the reaction mixture is stirred for 3 hours at RT. It is cooled again in an ice bath, a solution of 52.4 g of ethyl 4-bromobutanoate in 50 ml of THF is added dropwise and the mixture is stirred overnight at RT. It is concentrated under vacuum, the residue is taken up with water and extracted with ether, the organic phase is washed with water, with a buffer solution of pH 2, with water and with saturated NaCl solution and dried over MgSO4 and the solvent is evaporated off under vacuum. The residue is chromatographed on silica using toluene and then a toluene/AcOEt mixture (100/5; v/v) as the eluent to give 36.9 g of the expected product.

Workup

  1. temperaturecooled in an ice bath
  2. temperatureIt is cooled again in an ice bath
  3. stirringthe mixture is stirred overnight at RT
  4. concentrationIt is concentrated under vacuum
  5. extractionextracted with ether
  6. washthe organic phase is washed with water, with a buffer solution of pH 2, with water and with saturated NaCl solution
  7. dry with materialdried over MgSO4
  8. customthe solvent is evaporated off under vacuum
  9. customThe residue is chromatographed on silica

Sources & evidence

ORD record
ord-02387f9c4eb64c1f8e59cf5ee705b21b
Source dataset
uspto-grants-2000_02
Patent number
US06028082

Reaction notes

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