3-Pyridinecarboxaldehyde → Ethyl 5-(pyridin-3-yl)-2,4-pentadienoate

HRID 478733Notes

Reaction equation

HRID 478733 reaction equation
[Li+].CC([N-]C(C)C)C.C(=O)=O.CO.C(OP([CH2:22]/[CH:23]=[CH:24]/[C:25]([O:27][CH2:28][CH3:29])=[O:26])(OCC)=O)C.[CH:30](=O)[C:31]1[CH:36]=[CH:35][CH:34]=[N:33][CH:32]=1>C1COCC1.C(O)(=O)C>[N:33]1[CH:34]=[CH:35][CH:36]=[C:31]([CH:30]=[CH:22][CH:23]=[CH:24][C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:32]=1

Participants

7

Reactant 4

HCID 103713-PyridinecarboxaldehydeHCID 2724682Lithium diisopropylamideHCID 5365783Triethyl 4-phosphonocrotonate, mixture of isomersHCID 21973728Carbon dioxide methanol

Product 1

HCID 73177292Ethyl 5-(pyridin-3-yl)-2,4-pentadienoateYield 89,098.398%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of LDA (16.5 ml of 2M solution, 3.5 g, 0.03 mol) in THF (100 ml) was cooled to −70° C. or below (dry ice-methanol bath) under a nitrogen flow and treated dropwise with ethyl 4-diethylphosphonocrotonate (8.6 g, 0.037 mmol) while stirring. The mixture was further stirred for 15 minutes, treated dropwise with nicotinaldehyde (3.2 g, 0.030 mol), and then stirred at 0° C. for 1.5 hours. Next, the mixture was treated with acetic acid and evaporated. To the residue was added saturated aqueous sodium hydrogen carbonate and the mixture was extracted with ethyl acetate. The extract was treated according to conventional techniques. Evaporation of solvent yielded ethyl 5-(pyridin-3-yl)penta-2,4-dienoate as an oil (6.7 g).

Workup

  1. stirringThe mixture was further stirred for 15 minutes
  2. stirringstirred at 0° C. for 1.5 hours
  3. customevaporated
  4. additionTo the residue was added saturated aqueous sodium hydrogen carbonate
  5. extractionthe mixture was extracted with ethyl acetate
  6. additionThe extract was treated
  7. customEvaporation of solvent

Sources & evidence

ORD record
ord-b1e8fe4b02d94af8afeefda62785ac90
Source dataset
uspto-grants-2003_11
Patent number
US06642250B2

Reaction notes

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