Water → HCID 53782350, compound

HRID 1277985Notes

Reaction equation

HRID 1277985 reaction equation
[Na].C(OP(C(Br)C1C=CC(Cl)=CC=1)(=O)OCC)C.[CH2:19]([O:21][C:22]([CH:24]1[CH:26]([CH:27]=[C:28]([Br:36])[C:29]2[CH:34]=[CH:33][C:32]([Cl:35])=[CH:31][CH:30]=2)[C:25]1([CH3:38])[CH3:37])=[O:23])[CH3:20].C(OC([C@H]1[C@H](C=O)C1(C)C)=O)C.O>C(O)C.O1CCCC1>[CH2:19]([O:21][C:22]([CH:24]1[CH:26]([CH:27]=[C:28]([Br:36])[C:29]2[CH:34]=[CH:33][C:32]([Cl:35])=[CH:31][CH:30]=2)[C:25]1([CH3:37])[CH3:38])=[O:23])[CH3:20]

Participants

7

Reactant 4

HCID 962WaterHCID 5360545Sodium2×HCID 15882173Phosphonic acid, [bromo(4-chlorophenyl)methyl]-, diethyl esterHCID 131712296HCID 131712296, compound

Product 1

HCID 53782350HCID 53782350, compoundYield 48.3%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

4.6 g (0.2 mol) of sodium were dissolved in portions in 100 ml of ethanol. When all the sodium had dissolved, 100 ml of tetrahydrofuran (anhydrous) were added, and 68.3 g (0.2 mol) of 4-chloro-α-bromo-benzyl-phosphonic acid diethyl ester, dissolved in 50 ml of anhydrous tetrahydrofuran, were added dropwise at 0° C., whilst stirring. After the mixture had been subsequently stirred at 0°-5° C. for a further 2 hours, 34 g (0.2 mol) of cis/trans-2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid ethyl ester, dissolved in 50 ml of anhydrous tetrahydrofuran, were added dropwise at 0° C., whilst stirring. The mixture was then subsequently stirred at 20°-25° C. for a further 12 hours. 600 ml of water were then added to the reaction mixture and the mixture was extracted twice with 300 ml of methylene chloride each time. The organic phase was separated off and dried over magnesium sulphate, the solvent was distilled off under a waterpump vacuum and the residue was distilled in vacuo. 34.5 g (48.3% of theory) of 2,2-dimethyl-3-(2-bromo-2-(4-chloro-phenyl)-vinyl)-cyclopropanecarboxylic acid ethyl ester (cis, trans and E, Z isomer mixture) were obtained as a yellow oil with a boiling point of 160°-165° C./1 mm Hg.

Workup

  1. additionwere added dropwise at 0° C.
  2. stirringAfter the mixture had been subsequently stirred at 0°-5° C. for a further 2 hours
  3. additionwere added dropwise at 0° C.
  4. stirringwhilst stirring
  5. stirringThe mixture was then subsequently stirred at 20°-25° C. for a further 12 hours
  6. extractionthe mixture was extracted twice with 300 ml of methylene chloride each time
  7. customThe organic phase was separated off
  8. dry with materialdried over magnesium sulphate
  9. distillationthe solvent was distilled off under a waterpump vacuum
  10. distillationthe residue was distilled in vacuo

Sources & evidence

ORD record
ord-66282c4401614bd98aa4fe31a832244c
Source dataset
uspto-grants-1981_07
Patent number
US04279920

Reaction notes

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