Potassium Hydroxide → Ethyl alpha-(3,3-dichloroallyl)isovalerate

HRID 647551Notes

Reaction equation

HRID 647551 reaction equation
[CH:1]([C:4]([CH2:15][CH:16]=[C:17]([Cl:19])[Cl:18])(C(OCC)=O)[C:5]([O:7][CH2:8][CH3:9])=[O:6])([CH3:3])[CH3:2].[OH-].[K+].C(C(CC=C(Cl)Cl)(C(O)=O)C(O)=O)(C)C.C(C(CC=C(Cl)Cl)(C([O-])=O)C([O-])=O)(C)C.ClC(Cl)=CCC(C(C)C)C(O)=O>C(O)C.O>[Cl:18][C:17]([Cl:19])=[CH:16][CH2:15][CH:4]([CH:1]([CH3:3])[CH3:2])[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

8

Reactant 5

HCID 14797Potassium HydroxideHCID 12959689HCID 12959689, compound2×HCID 129596915,5-Dichloro-2-isopropyl-4-pentenoic acidHCID 20485209HCID 20485209, compoundHCID 86739062HCID 86739062, compound

Product 1

HCID 12959690Ethyl alpha-(3,3-dichloroallyl)isovalerate

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

In 20 g of ethanol were dissolved 8.8 g of the above diethyl isopropyl-(3,3-dichloroallyl)malonate and a solution of 6.4 g of potassium hydroxide in 10 g of water was added to the above ethanol solution. The mixture was refluxed overnight. Then, the reaction mixture was distilled to remove the ethanol and a sufficient amount of dilute hydrochloric acid was added to make the residue acidic. The residue was extracted with diethyl ether and the ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By this procedure there was obtained a mixture of isopropyl-(3,3-dichloroallyl)malonic acid and morbethyl isopropyl-(3,3-dichloroallyl)malonate. This mixture was subjected to decarboxylation reaction at 180° to 230° C. under a reduced pressure of 35 to 60 mmHg, whereupon 6.0 g of a mixture of α-(3,3-dichloroallyl) isovaleric acid and ethyl α-(3,3-dichloroallyl)isovalerate was obtained. In 20 g of ethanol were dissolved 6.0 g of the above decarboxylated mixture and a solution of 1.2 g of sodium hydroxide in 10 g of water was added to the above solution. The mixture was refluxed for 4 hours, after which the ethanol was distilled off. The residue was made acidic with dilute hydrochloric acid and extracted with diethyl ether. The ethereal layer was dried over anhydrous magnesium sulfate and distilled to remove the low-boiling fraction. By the above procedure there were obtained 4.2 g of α-(3,3-dichloroallyl)isovaleric acid, the NMR spectrum of which appears below [yield: 70% based on diethyl isopropyl-(3,3-dichloroallyl)malonate].

Workup

  1. temperatureThe mixture was refluxed overnight
  2. distillationThen, the reaction mixture was distilled
  3. customto remove the ethanol
  4. additiona sufficient amount of dilute hydrochloric acid was added
  5. extractionThe residue was extracted with diethyl ether
  6. dry with materialthe ethereal layer was dried over anhydrous magnesium sulfate
  7. distillationdistilled
  8. customto remove the low-boiling fraction
  9. customBy this procedure there was obtained

Sources & evidence

ORD record
ord-d1f118efe72a408ca32f75437bf2c2ed
Source dataset
uspto-grants-1983_10
Patent number
US04409238

Reaction notes

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