Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → HCID 11334330, compound

HRID 508657Notes

Reaction equation

HRID 508657 reaction equation
[Br:1][C:2]1[N:7]=[CH:6][C:5]([CH:8]=O)=[CH:4][CH:3]=1.[C:10]([CH:15]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:12][CH2:13][CH3:14])=[O:11]>C1(C)C=CC=CC=1>[Br:1][C:2]1[N:7]=[CH:6][C:5](/[CH:8]=[CH:15]/[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 117692346-Bromo-3-pyridinecarboxaldehyde

Product 1

HCID 11334330HCID 11334330, compoundYield 97.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 6-bromo-3-pyridinecarboxaldehyde (3.06 g, 15.63 mmol) and (carbethoxymethylene)triphenylphosphorane (6.60 g, 17.97 mmol) in toluene (45 mL) was heated at reflux overnight and then cooled to room temperature. After solvent removal at reduced pressure, the residue was chromatographed (16% EtOAc/hexane) to give 3.9 g (97%) of ethyl(E)-3-(6-bromo-3-pyridinyl)-2-propenoate as a pale-yellow solid. Recrystallization from hexane yielded 3.5 g (87%) of pure E-isomer as a white solid, mp 79-80° C. By comparison, the material prepared by the literature method (van den Heuvel, M., et al., J. Org. Chem., 2004, 69, 250-262) had a melting point of 83.6-84.1° C. IR 2979, 1709, 1462, 1179 cm−1; 1H NMR (CDCl3) δ 1.36 (t, J=7.2 Hz, 3H, OCH2CH3), 4.31 (q, J=7.2 Hz, 2H, OCH2CH3), 6.53 (d, J=16.2 Hz, 1H, CH═CHCO), 7.55 (d, J=8.1 Hz, 1H, 5-ArH), 7.68 (d, J=16.2 Hz, 1H, CH═CHCO), 7.72 (dd, J=2.1 Hz, 8.1 Hz, 1H, 4-ArH), 8.52 ppm (d, J=2.1 Hz, 1H, 2-ArH).

Workup

  1. temperatureat reflux overnight
  2. customAfter solvent removal at reduced pressure
  3. customthe residue was chromatographed (16% EtOAc/hexane)

Sources & evidence

ORD record
ord-09023c199be14e8490c01364f0bb1502
Source dataset
uspto-grants-2015_08
Patent number
US09096544B2

Reaction notes

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