Ethyl cyanoacetate → Ethyl 1-cyano-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate

HRID 894493Notes

Reaction equation

HRID 894493 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].[Cl:9][C:10]([Cl:18])=[CH:11][CH:12](Cl)[C:13](Cl)([CH3:15])[CH3:14].ClC(Cl)=CC=C(C)C>C(#N)C>[C:1]([C:3]1([C:4]([O:6][CH2:7][CH3:8])=[O:5])[CH:12]([CH:11]=[C:10]([Cl:18])[Cl:9])[C:13]1([CH3:15])[CH3:14])#[N:2]

Participants

5

Reactant 3

HCID 7764Ethyl cyanoacetateHCID 1087461,3-Pentadiene, 1,1-dichloro-4-methyl-HCID 133590071,1,3,4-Tetrachloro-4-methylpent-1-ene

Product 1

HCID 12898169Ethyl 1-cyano-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A mixture of ethyl cyanoacetate (12.44 parts), 1,1,3,4-tetrachloro-4-methylpent-1-ene (11.1 parts), 1,1-dichloro-4-methylpenta-1,3-diene (7.55 parts), cupric acetate H2O (2.0 parts) and in two cases lithium halide, in acetonitrile (100 parts by volume) is heated to reflux and held at 75°-80° C. for 6 hours. After cooling to room temperature the suspension is filtered and the residue is washed twice with acetonitrile (20 parts by volume). The combined filtrate and washes are distilled under reduced pressure to remove acetonitrile and the residue is extracted with a mixture of toluene (100 parts by volume), water (150 parts by volume) and concentrated hydrochloric acid (100 parts by volume). After filtering from extraneous matter the filtrates are separated and the toluene layer is washed twice with hydrochloric acid (50 parts by volume) diluted with water (50 parts) and finally four times with water (50 parts). The toluene is removed by distillation under reduced pressure to yield crude ethyl 1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate. Details are given in the following table:

Workup

  1. temperatureto reflux
  2. filtrationis filtered
  3. washthe residue is washed twice with acetonitrile (20 parts by volume)
  4. distillationThe combined filtrate and washes are distilled under reduced pressure
  5. customto remove acetonitrile
  6. extractionthe residue is extracted with a mixture of toluene (100 parts by volume), water (150 parts by volume) and concentrated hydrochloric acid (100 parts by volume)
  7. filtrationAfter filtering from extraneous matter the filtrates
  8. customare separated
  9. washthe toluene layer is washed twice with hydrochloric acid (50 parts by volume)
  10. additiondiluted with water (50 parts) and finally four times with water (50 parts)
  11. customThe toluene is removed by distillation under reduced pressure

Sources & evidence

ORD record
ord-aa5f0601928e4bb7bb7252f0199b268e
Source dataset
uspto-grants-1981_08
Patent number
US04284582

Reaction notes

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