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

HRID 1241710Notes

Reaction equation

HRID 1241710 reaction equation
[Li+].[CH3:2]C([N-]C(C)C)C.C(=O)=O.CO.[CH3:14][CH2:15][O:16][C:17](/[CH:19]=[CH:20]/[CH2:21]P(OCC)(OCC)=O)=[O:18].C(=O)[C:31]1[CH:36]=[CH:35][N:34]=[CH:33][CH:32]=1>C1COCC1.C(O)(=O)C>[N:34]1[CH:33]=[CH:32][CH:31]=[C:36]([CH:2]=[CH:21][CH:20]=[CH:19][C:17]([O:16][CH2:15][CH3:14])=[O:18])[CH:35]=1

Participants

7

Reactant 4

HCID 133894-PyridinecarboxaldehydeHCID 2724682Lithium diisopropylamideHCID 5365783Triethyl 4-phosphonocrotonate, mixture of isomersHCID 21973728Carbon dioxide methanol

Product 1

HCID 73177292Ethyl 5-(pyridin-3-yl)-2,4-pentadienoate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of LDA (16.5 ml of 2M solution, 3.5 g, 0.033 mol) in THF (100 ml) was cooled to −78° C. or below (dry ice-methanol bath) under a nitrogen flow and treated dropwise with triethyl 4-phosphonocrotonate (8.6 g, 0.037 mmol) while stirring. The mixture was further stirred for 15 minutes, treated dropwise with isonicotinaldehyde (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)-2,4-pentadienoate as a crystalline product (3.3 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-b22f7c81285143148ddf03dc6a3ef9dd
Source dataset
uspto-grants-2006_10
Patent number
US07115623B2

Reaction notes

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