2,3-Dichloropropene → Ethyl 4-chloro-2,2-dimethylpent-4-enoate

HRID 1975731Notes

Reaction equation

HRID 1975731 reaction equation
C(N[CH:5]([CH3:7])[CH3:6])(C)C.C([Li])CCC.[C:13]([O:18][CH2:19][CH3:20])(=[O:17])[CH:14]([CH3:16])[CH3:15].[Cl:21]C(CCl)=C>C1COCC1>[Cl:21][C:5](=[CH2:6])[CH2:7][C:14]([CH3:16])([CH3:15])[C:13]([O:18][CH2:19][CH3:20])=[O:17]

Participants

6

Reactant 4

HCID 65652,3-DichloropropeneHCID 7342Ethyl isobutyrateHCID 7912DiisopropylamineHCID 178418339Butyllithium

Product 1

HCID 3653118Ethyl 4-chloro-2,2-dimethylpent-4-enoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of diisopropylamine (126.5 g; 1.25 mol) in 1500 mL THF at -78° C. was added n-butyllithium (500 mL of a 2.5M solution in hexanes). Upon completion of addition, the mixture was stirred for 30 minutes. A solution of ethyl isobutyrate (132 g; 1.14 mol) in 300 mL THF was added slowly over about 1 hour. The reaction was then allowed to stir for an additional hour at -78° C. 2,3-Dichloro-1-propene (138.7 g; 1.25 mol) was added dropwise. The cooling bath was removed and the reaction was stirred at ambient temperature for 15 hours. Saturated aqueous ammonium chloride solution was added and the THF was removed in vacuo. The aqueous residue was then extracted with ethyl acetate. The extracts were dried over magnesium sulfate and concentrated. Distillation yielded ethyl 4-chloro-2,2-dimethyl-4-pentenoate as a colorless liquid (b.p. 100°-104° C./30 torr).

Workup

  1. additionUpon completion of addition
  2. stirringto stir for an additional hour at -78° C
  3. customThe cooling bath was removed
  4. stirringthe reaction was stirred at ambient temperature for 15 hours
  5. additionSaturated aqueous ammonium chloride solution was added
  6. customthe THF was removed in vacuo
  7. extractionThe aqueous residue was then extracted with ethyl acetate
  8. dry with materialThe extracts were dried over magnesium sulfate
  9. concentrationconcentrated
  10. distillationDistillation

Sources & evidence

ORD record
ord-4e2f8cf2b12a4610bfcf22f7aaf98422
Source dataset
uspto-grants-1994_02
Patent number
US05288743

Reaction notes

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