Carbon Tetrachloride → Ethyl 3-[2-chloro-2-(4-chlorophenyl)ethenyl]-2,2-dimethylcyclopropanecarboxylate

HRID 905246Notes

Reaction equation

HRID 905246 reaction equation
C(OP([CH2:9][C:10]1[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][CH:11]=1)(=O)OCC)C.C([Li])CCC.C(Cl)(Cl)(Cl)[Cl:23].[CH2:27]([O:29][C:30]([CH:32]1[CH:34]([CH:35]=O)[C:33]1([CH3:38])[CH3:37])=[O:31])[CH3:28]>O1CCCC1.O>[CH2:27]([O:29][C:30]([CH:32]1[CH:34]([CH:35]=[C:9]([Cl:23])[C:10]2[CH:11]=[CH:12][C:13]([Cl:16])=[CH:14][CH:15]=2)[C:33]1([CH3:38])[CH3:37])=[O:31])[CH3:28]

Participants

7

Reactant 4

HCID 5943Carbon TetrachlorideHCID 99240Diethyl 4-chlorobenzylphosphonateHCID 566079Ethyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylateHCID 178418339Butyllithium

Product 1

HCID 54387129Ethyl 3-[2-chloro-2-(4-chlorophenyl)ethenyl]-2,2-dimethylcyclopropanecarboxylateYield 54.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

26.3 g (0.1 mol) of 4-chlorobenzyl-phosphonic acid diethyl ester were dissolved in 400 ml of absolute tetrahydrofuran and the solution was cooled to -70° C. 0.11 mol of n-butyl-lithium (15% strength solution in hexane) were added dropwise, in counter-current with nitrogen and while stirring thoroughly, and the reaction mixture was then subsequently stirred at -70° C. for a further 15 minutes. 15.4 g (0.1 mol) of carbon tetrachloride were then added dropwise at -70° C., also under nitrogen, and the reaction mixture thereby became red-brown in color. After stirring for a further 15 minutes, 18.6 g (0.1 mol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid ethyl ester were added at -65° C. The reaction mixture was then allowed to come to room temperature and was subsequently stirred at 25° C. for a further 3 hours. The reaction mixture was then poured into 2 liters of water and extracted with 600 ml of ether. The ether phase was dried over sodium sulphate, the solvent was stripped off in vacuo and the oily residue was distilled at 150°-155° C./2 mm Hg. 2,2-Dimethyl-3-(2-chloro-2-p-chlorophenyl-vinyl)-cyclopropanecarboxylic acid ethyl ester was obtained in 54.3% yield.

Workup

  1. stirringthe reaction mixture was then subsequently stirred at -70° C. for a further 15 minutes
  2. stirringAfter stirring for a further 15 minutes
  3. customto come to room temperature
  4. stirringwas subsequently stirred at 25° C. for a further 3 hours
  5. extractionextracted with 600 ml of ether
  6. dry with materialThe ether phase was dried over sodium sulphate
  7. distillationthe oily residue was distilled at 150°-155° C./2 mm Hg

Sources & evidence

ORD record
ord-7417f66d838f4feeb60606f21268b02c
Source dataset
uspto-grants-1983_12
Patent number
US04423066

Reaction notes

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