Acetic Acid → Ethyl 2-cyano-4,4-dimethylpent-2-enoate

HRID 375102Notes

Reaction equation

HRID 375102 reaction equation
[CH3:1][C:2]([CH:5]=O)([CH3:4])[CH3:3].[CH2:7]([O:9][C:10](=[O:14])[CH2:11][C:12]#[N:13])[CH3:8].C(O)(=O)C.N1C=CC=CC=1>Cl>[CH2:7]([O:9][C:10](=[O:14])[C:11]([C:12]#[N:13])=[CH:1][C:2]([CH3:5])([CH3:4])[CH3:3])[CH3:8]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 1049PyridineHCID 7764Ethyl cyanoacetateHCID 12417Pivalaldehyde2×

Product 1

HCID 53661853Ethyl 2-cyano-4,4-dimethylpent-2-enoateYield 73.2%

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

A mixture of pivaldehyde (5.00 g, 58 mmol), ethylcyanoacetate (6.60g, 58.3 mmol), acetic acid (3.50 g, 58.3 mmol) and pyridine (4.60 g, 58.2 mmol) was heated at reflux for 1 h. A second portion of pivaldehyde (5.00 g, 58 mmol) was added. The refluxing of the mixture was continued for 18h. After cooling, the mixture was poured into 1N aqueous HCl (50 mL). The resulting mixture was extracted with EtOAc (3×50 mL). The combined organic layers, were washed with 1N aqueous HCl, dried (MgSO4) and concentrated to give a colorless oil. The oil was purified by flash chromatography on SiO2 using hexane-EtOAc (9:1) as the eluant to give 2-cyano-4,4-dimethyl-2-pentenoic acid ethyl ester as a colorless oil (7.69 g, 73 % yield).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1 h
  3. temperatureThe refluxing of the mixture
  4. temperatureAfter cooling
  5. extractionThe resulting mixture was extracted with EtOAc (3×50 mL)
  6. washThe combined organic layers, were washed with 1N aqueous HCl
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. customto give a colorless oil
  10. customThe oil was purified by flash chromatography on SiO2

Sources & evidence

ORD record
ord-3a447c8db62f4639b43b05ce57a7ad71
Source dataset
uspto-grants-1996_01
Patent number
US05484771

Reaction notes

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