Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → 3-[5-Chloro-6-(cyano-dimethyl-methyl)-pyridin-3-yl]-acrylic acid ethyl ester

HRID 1438311Notes

Reaction equation

HRID 1438311 reaction equation
[Cl:1][C:2]1[C:3]([C:10]([CH3:14])([CH3:13])[C:11]#[N:12])=[N:4][CH:5]=[C:6]([CH:8]=O)[CH:7]=1.[C:15]([CH:20]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:17][CH2:18][CH3:19])=[O:16]>C1COCC1>[CH2:18]([O:17][C:15](=[O:16])[CH:20]=[CH:8][C:6]1[CH:5]=[N:4][C:3]([C:10]([C:11]#[N:12])([CH3:14])[CH3:13])=[C:2]([Cl:1])[CH:7]=1)[CH3:19]

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 587642732-(3-Chloro-5-formyl-pyridin-2-yl)-2-methyl-propionitrile

Product 1

HCID 670843503-[5-Chloro-6-(cyano-dimethyl-methyl)-pyridin-3-yl]-acrylic acid ethyl esterYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 2-(3-chloro-5-formyl-pyridin-2-yl)-2-methyl-propionitrile (0.58 g, 2.78 mmol) from step 3 above and (carbethoxymethylene)triphenylphosphorane (1.26 g, 3.61 mmol) in dry THF (12 mL) was heated to 55° C. and maintained at this temperature overnight. The solvents were removed and the residue was purified by flash column chromatography (0-20% EtOAc in hexanes) to give the product (0.74 g, 96% yield) as a white solid. 1H NMR (400 MHz, CDCl3): δ 1.35 (t, J=7.7 Hz, 3H), 1.87 (s, 6H), 4.29 (q, J=14, 7.7 Hz, 2H), 6.53 (d, J=16 Hz, 1H), 7.65 (d, J=16 Hz, 1H), 7.87 (d, J=2 Hz, 1H), 8.58 (d, J=2 Hz, 1H). ESIMS (MH+): 279.

Workup

  1. temperaturemaintained at this temperature overnight
  2. customThe solvents were removed
  3. customthe residue was purified by flash column chromatography (0-20% EtOAc in hexanes)

Sources & evidence

ORD record
ord-7896c551539044feb36536c7c957aa02
Source dataset
uspto-grants-2009_11
Patent number
US07622605B2

Reaction notes

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