Ethyl Acetate → Ethyl 2-(3,4-dichlorobenzyl)-3-oxobutanoate

HRID 1503230Notes

Reaction equation

HRID 1503230 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[H-].[Na+].[Cl:12][C:13]1[CH:14]=[C:15]([CH:18]=[CH:19][C:20]=1[Cl:21])[CH2:16]Br.C(OCC)(=O)C>O1CCCC1.O>[C:3]([CH:2]([CH2:16][C:15]1[CH:18]=[CH:19][C:20]([Cl:21])=[C:13]([Cl:12])[CH:14]=1)[C:1]([O:7][CH2:8][CH3:9])=[O:6])(=[O:4])[CH3:5]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 8868Ethyl AcetoacetateHCID 24758Sodium hydrideHCID 6397264-(Bromomethyl)-1,2-dichlorobenzene

Product 1

HCID 67402529Ethyl 2-(3,4-dichlorobenzyl)-3-oxobutanoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of ethyl acetoacetate (1.0 g) in tetrahydrofuran (20 mL) was added sodium hydride (about 60% oil suspension) (0.37 g) in several portions under ice-cooling under a nitrogen atmosphere. After stirring at room temperature for 1 hr, 3,4-dichlorobenzylbromide (1.4 mL) was added to the reaction mixture. After stirring at room temperature for 2 hr, the reaction mixture was poured into a mixture of ethyl acetate and water. The organic phase was washed successively with water and brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by column chromatography on silica gel by eluting with toluene. An eluted fraction containing the desired product was recovered and evaporated under reduced pressure to give ethyl 2-acetyl-3-(3,4-dichlorophenyl)propanoate (35) (1.6 g).

Workup

  1. temperaturecooling under a nitrogen atmosphere
  2. stirringAfter stirring at room temperature for 2 hr
  3. washThe organic phase was washed successively with water and brine
  4. dry with materialdried over magnesium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customthe residue was purified by column chromatography on silica gel
  7. washby eluting with toluene
  8. additionAn eluted fraction containing the desired product
  9. customwas recovered
  10. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-95f5cc8ad77446eda9277125689b4636
Source dataset
uspto-grants-2015_12
Patent number
US09212169B2

Reaction notes

Loading…