Pyridine → 2,2-Dimethyl-3-oxo-5-pyridin-4-yl-pent-4-enenitrile

HRID 2223096Notes

Reaction equation

HRID 2223096 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH:7]=O)=[CH:3][CH:2]=1.N1C=CC=CC=1.[CH3:15][C:16]([CH3:22])([C:19](=[O:21])[CH3:20])[C:17]#[N:18].C(NCC)C>C(OCC)(=O)C.O>[CH3:15][C:16]([CH3:22])([C:19](=[O:21])[CH:20]=[CH:7][C:4]1[CH:3]=[CH:2][N:1]=[CH:6][CH:5]=1)[C:17]#[N:18]

Participants

7

Reactant 4

HCID 1049PyridineHCID 8021DiethylamineHCID 133894-PyridinecarboxaldehydeHCID 124683092,2-Dimethyl-3-oxobutanenitrile

Product 1

HCID 691376492,2-Dimethyl-3-oxo-5-pyridin-4-yl-pent-4-enenitrileYield 59%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

Pyridine-4-carboxaldehyde (6.9 ml, 72 mmol) was added to dry pyridine (16 ml) under argon. 2,2-Dimethyl-3-oxo-butyronitrile {J. K. Rasmussen et al., Synthesis, 1973, 682} (8.0 g, 72 mmol) and diethylamine (7.3 ml, 71 mmol) were subsequently added and the solution heated under reflux for 18 hours. After cooling to room temperature, the mixture was poured into water and ethyl acetate. The mixture was separated and the aqueous phase re-extracted with ethyl acetate. The combined organic layers were dried and concentrated in vacuo to yield a solid which was triturated with diethyl ether to give the title compound (8.5 g, 59%); MS (ES+) m/e 201 [M+H]+.

Workup

  1. additionwere subsequently added
  2. temperaturethe solution heated
  3. temperatureunder reflux for 18 hours
  4. customThe mixture was separated
  5. extractionthe aqueous phase re-extracted with ethyl acetate
  6. customThe combined organic layers were dried
  7. concentrationconcentrated in vacuo
  8. customto yield a solid which
  9. customwas triturated with diethyl ether

Sources & evidence

ORD record
ord-d5300a5ebe9c40e7a60c0c58261e9f58
Source dataset
uspto-grants-2008_05
Patent number
US07375105B2

Reaction notes

Loading…