Dimethyl Sulfide → 6-Ethyl-5-(2-oxo-ethyl)-pyridin-3-yl-acetic acid methyl ester

HRID 900977Notes

Reaction equation

HRID 900977 reaction equation
[CH3:1][O:2][C:3](=[O:16])[CH2:4][C:5]1[CH:6]=[N:7][C:8]([CH2:14][CH3:15])=[C:9]([CH2:11][CH:12]=C)[CH:10]=1.[O:17]=[O+][O-].CSC>CO.ClCCl>[CH3:1][O:2][C:3](=[O:16])[CH2:4][C:5]1[CH:6]=[N:7][C:8]([CH2:14][CH3:15])=[C:9]([CH2:11][CH:12]=[O:17])[CH:10]=1

Participants

6

Reactant 3

HCID 1068Dimethyl SulfideHCID 24823OzoneHCID 596988185-Allyl-6-ethyl-pyridin-3-yl-acetic acid methyl ester

Product 1

HCID 596987946-Ethyl-5-(2-oxo-ethyl)-pyridin-3-yl-acetic acid methyl esterYield 78%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 5-allyl-6-ethyl-pyridin-3-yl-acetic acid methyl ester (1.00 g, 4.56 mmol) in 50% methanol in dichloromethane solution (25 mL, 0.2 M) is cooled to −78° C. and treated with ozone. After the solution became blue (30 min), it is purged with nitrogen and treated with dimethyl sulfide (1.7 mL, 23 mmol). After stirring overnight the solvent is removed in vacuo and the product is purified by flash chromatography (50% ethyl acetate in n-heptane) to provide 6-ethyl-5-(2-oxo-ethyl)-pyridin-3-yl-acetic acid methyl ester as a clear oil (0.78 g, 78%): Rf 0.26 (50% ethyl acetate in n-heptane), 1H NMR (CDCl3, 300 MHz) δ 9.77 (s, 1 H), 8.41 (s, 1 H), 7.43 (s, 1 H), 3.76 (s, 2 H), 3.72 (s, 3 H), 3.62 (s, 2 H), 2.77 (q, J=7.5 Hz, 2H), 1.27 (t, J=7.5 Hz, 3H). ESI-LCMS m/z calcd for C12H15NO3: 221.1; found 222.0 (M+1)+.

Workup

  1. custom(30 min), it
  2. customis purged with nitrogen
  3. customis removed in vacuo
  4. customthe product is purified by flash chromatography (50% ethyl acetate in n-heptane)

Sources & evidence

ORD record
ord-df382f1bf0944392b19aa9bf69414322
Source dataset
uspto-grants-2008_04
Patent number
US07361671B2

Reaction notes

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