Methanol → HCID 20349359, compound

HRID 1449387Notes

Reaction equation

HRID 1449387 reaction equation
Cl[C:2]1[CH:7]=[C:6]([C:8]([Cl:11])([Cl:10])[Cl:9])[CH:5]=[C:4]([O:12][CH2:13][CH3:14])[N:3]=1.[Na].[CH3:16][OH:17]>>[CH3:16][O:17][C:2]1[CH:7]=[C:6]([C:8]([Cl:11])([Cl:10])[Cl:9])[CH:5]=[C:4]([O:12][CH2:13][CH3:14])[N:3]=1

Participants

4

Reactant 3

HCID 887Methanol3×HCID 5360545Sodium2×HCID 23467924HCID 23467924, compound

Product 1

HCID 20349359HCID 20349359, compound

Conditions

Temperature
62 °C

Procedure

To a solution of 54.99 grams (0.20 mole) of 2-chloro-6-ethoxy-4-(trichloromethyl)pyridine dissolved in 100 ml of methanol at 60° C. was rapidly added a solution of 6.90 grams (0.3 mole) of sodium metal dissolved in 150 ml of methanol. The mixture was heated to reflux for ~1 hour and then stirred at 62° C. overnight and thereafter refluxed for 8 hours followed by stirring at 62° C. overnight and then refluxed for 1 hour. A solution of 3.45 grams of sodium metal dissolved in 75 ml of methanol was added and the mixture brought back to reflux. The mixture was thereafter cooled and covered and allowed to sit ~64 hours (over a weekend). The methanol was removed by evaporation and the residue diluted with water and extracted with methylene chloride. The extract was washed with water, dried with sodium sulfate and the methylene chloride removed by evaporation. The desired 2-methoxy-6-ethoxy-4-(trichloromethyl)pyridine product was recovered by crystallization of the residue from methanol followed by recrystallization from ethanol. The product was recovered in a yield of 8.5 grams and melted at 36°-38° C. Upon analysis, the product was found to have carbon, hydrogen, nitrogen and chlorine contents of 39.49, 3.54, 5.17 and 39.82 percent, respectively, as compared with the theoretical contents of 39.95, 3.72, 5.17 and 39.31 percent, respectively, as calculated for the above-named compound.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for ~1 hour
  3. temperaturerefluxed for 8 hours
  4. stirringby stirring at 62° C. overnight
  5. temperaturerefluxed for 1 hour
  6. additionwas added
  7. temperatureto reflux
  8. temperatureThe mixture was thereafter cooled
  9. waitto sit ~64 hours
  10. custom(over a weekend)
  11. customThe methanol was removed by evaporation
  12. additionthe residue diluted with water
  13. extractionextracted with methylene chloride
  14. washThe extract was washed with water
  15. dry with materialdried with sodium sulfate
  16. customthe methylene chloride removed by evaporation
  17. customThe desired 2-methoxy-6-ethoxy-4-(trichloromethyl)pyridine product was recovered by crystallization of the residue from methanol
  18. customfollowed by recrystallization from ethanol
  19. customThe product was recovered in a yield of 8.5 grams and melted at 36°-38° C

Sources & evidence

ORD record
ord-550872f56083498cb8d89b52712420d4
Source dataset
uspto-grants-1980_02
Patent number
US04190662

Reaction notes

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