Acetic Acid → (4,6-Dimethylpyridin-2-yl)methyl acetate

HRID 747344Notes

Reaction equation

HRID 747344 reaction equation
[N:1]1[C:6]([CH3:7])=[CH:5][C:4]([CH3:8])=[CH:3][C:2]=1[CH3:9].OO.[C:12]([OH:15])(=[O:14])[CH3:13]>C(OC(=O)C)(=O)C>[C:12]([O:15][CH2:9][C:2]1[CH:3]=[C:4]([CH3:8])[CH:5]=[C:6]([CH3:7])[N:1]=1)(=[O:14])[CH3:13]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 784Hydrogen Peroxide2×HCID 79532,4,6-Trimethylpyridine

Product 1

HCID 585970(4,6-Dimethylpyridin-2-yl)methyl acetateYield 24%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Procedure

To a stirred solution of 2,4,6-collidine (3.22 g, 26.6 mmol) in glacial acetic acid (21 mL) at room temperature was added 30% H2O2 (3.0 mL) and the resultant solution was heated to 70° C. After 6 hours, the reaction mixture was cooled to room temperature, additional H2O2 (3.0 mL) was added, and the solution was heated at 70° C. overnight. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in CHCl3 (50 mL) and treated with solid Na2CO3 (9.9 g). After 1 hour, the supernatant was decanted and the residue was washed with warm CHCl3 (3×75 mL). The combined supernatants were filtered and concentrated to provide 2.43 g as a yellow oil. The oil was dissolved in acetic anhydride (22.5 mL) and heated at 90° C. overnight. The mixture was cooled to room temperature and concentrated. The crude product was purified by flash chromatography (40 g silica gel, 2:1 hexanes/ethyl acetate) to give 1.05 g (24%) of 2-acetoxymethyl-4,6-dimethylpyridine: 1H NMR (CDCl3) □ 2.31 (s, 3H), 2.35 (s, 3H), 2.51 (s, 3H), 5.14 (s, 2H), 6.92 (s, 1H), 6.97 (s, 1H); and 0.35 g (8%) of 4-acetoxymethyl-2,5-dimethylpyridine: 1H NMR (CDCl3) □ 2.15 (s, 3H), 2.53 (s, 6H), 5.04 (s, 2H), 6.92 (s, 2H).

Workup

  1. temperaturethe solution was heated at 70° C. overnight
  2. temperatureThe reaction mixture was cooled to room temperature
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe residue was dissolved in CHCl3 (50 mL)
  5. additiontreated with solid Na2CO3 (9.9 g)
  6. waitAfter 1 hour
  7. customthe supernatant was decanted
  8. washthe residue was washed with warm CHCl3 (3×75 mL)
  9. filtrationThe combined supernatants were filtered
  10. concentrationconcentrated
  11. customto provide 2.43 g as a yellow oil
  12. temperatureheated at 90° C. overnight
  13. temperatureThe mixture was cooled to room temperature
  14. concentrationconcentrated
  15. customThe crude product was purified by flash chromatography (40 g silica gel, 2:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-1e7798cb8a54477bb521c8c5d57bb25f
Source dataset
uspto-grants-2008_07
Patent number
US07396840B2

Reaction notes

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