Ethyl cyanoacetate → Cyclopropanecarboxylic acid, 1-cyano-2-ethenyl-, ethyl ester

HRID 637245

Reaction equation

HRID 637245 reaction equation
[CH2:1](Cl)/[CH:2]=[CH:3]/[CH2:4]Cl.[C:7]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])#[N:8].[Cl-].C(C([NH3+])(C(=O)CCCCCCC)C(=O)CCCCCCC)(=O)CCCCCCC.[OH-].[K+]>C1C=CC=CC=1>[CH:2]([CH:3]1[CH2:4][C:9]1([C:7]#[N:8])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH2:1]

Participants

6

Reactant 4

HCID 7764Ethyl cyanoacetateHCID 14797Potassium Hydroxide2×HCID 6421971,4-Dichloro-2-butene, (2E)-HCID 77620884Tricaprylylmethyl ammonium chloride

Product 1

HCID 564450Cyclopropanecarboxylic acid, 1-cyano-2-ethenyl-, ethyl ester

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Ethyl 2-vinyl-1-cyanocyclopropane-1-carboxylate was prepared in accordance with the procedure of U.S. Pat. No. 4,252,739. For the reaction 750 ml benzene, 250 gms (2 moles) 1,4-dichlorobutene-2, 113 gms (1 mole) ethyl cyanoacetate and 3 gms tricaprylylmethylammonium chloride were charged to a reactor and heated to reflux with agitation. Potassium hydroxide (85%) pellets (132 gms; 2 moles) were then added to the stirred solution in small portions. A mild exotherm was observed with the addition of caustic and external cooling was provided as necessary to maintain mild reflux. When the KOH addition was complete the reaction was stirred at reflux for 5 hours while removing water by azeotropic distillation. The reaction mixture was then filtered and the benzene evaporated. Distillation under reduced pressure yielded ethyl 2-vinyl-1-cyanocyclopropane-1-carboxylate (B.p. 55° C. at 0.02 mm Hg, lit. 112° C. at 11 mm Hg.; nD25° 1.4661, lit. nD24° 1.4650).

Workup

  1. customEthyl 2-vinyl-1-cyanocyclopropane-1-carboxylate was prepared in accordance with the procedure of U.S
  2. additionwere charged to a reactor
  3. temperatureheated
  4. temperatureto reflux with agitation
  5. additionA mild exotherm was observed with the addition of caustic and
  6. temperatureexternal cooling
  7. customwas provided as necessary
  8. temperatureto maintain mild reflux
  9. temperatureat reflux for 5 hours
  10. customwhile removing water
  11. distillationby azeotropic distillation
  12. filtrationThe reaction mixture was then filtered
  13. customthe benzene evaporated
  14. distillationDistillation under reduced pressure

Sources & evidence

ORD record
ord-a12362b6af4147979a6c4a7d88af3389
Source dataset
uspto-grants-1985_12
Patent number
US04556409

Linked notes

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