Ethanol → HCID 20349360, compound

HRID 1449385Notes

Reaction equation

HRID 1449385 reaction equation
[Na].Cl[C:3]1[N:8]=[C:7]([O:9][CH2:10][CH3:11])[CH:6]=[C:5]([C:12]([Cl:15])([Cl:14])[Cl:13])[CH:4]=1.[Cl-].[NH4+].[CH2:18]([OH:20])[CH3:19]>O>[CH2:10]([O:9][C:7]1[CH:6]=[C:5]([C:12]([Cl:15])([Cl:14])[Cl:13])[CH:4]=[C:3]([O:20][CH2:18][CH3:19])[N:8]=1)[CH3:11]

Participants

6

Reactant 4

HCID 702Ethanol3×HCID 25517Ammonium ChlorideHCID 5360545Sodium2×HCID 23467924HCID 23467924, compound

Product 1

HCID 20349360HCID 20349360, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution was prepared by dissolving 17.24 grams (0.75 mole) of sodium metal in 400 ml of ethanol. To this solution was rapidly added a solution prepared by dissolving 137.48 grams (0.5 mole) of 6-chloro-2-ethoxy-4-(trichloromethyl)pyridine in 300 ml of ethanol at 35° C. The mixture was heated to reflux at 72° for ~42 hours and thereafter a solution of 8.62 grams of sodium metal dissolved in 200 ml of ethanol was added thereto and the mixture refluxed for about an additional 5 hours. The mixture was diluted with 500 ml of water after first removing 500 ml of ethanol. The mixture was extracted twice with methylene chloride and the methylene chloride layers combined and washed with water (an emulsion formed and ammonium chloride was added thereto and the mixture allowed to set 3 days (week-end) for the emulsion to break). The methylene chloride layer was dried over sodium sulfate, treated with activated charcoal and filtered. The methylene chloride was removed by evaporation and 150 ml of methanol was added thereto. The mixture was chilled and the 2,6-diethoxy-4-(trichloromethyl)pyridine product which precipitated was separated. The product was recrystallized from 150 ml of methanol and dried over methylene chloride. The product melted at 45.5°-47.0° C. and was recovered in a yield of 46 grams (32 percent of theoretical). The product was found by analysis to have carbon, hydrogen, and nitrogen contents of 42.12, 4.17 and 4.92 percent, respectively, as compared with the theoretical contents of 42.20, 4.25 and 4.92 percent, respectively, as calculated for the above-named compound. The structure of the compound was confirmed by NMR.

Workup

  1. customA solution was prepared
  2. additionTo this solution was rapidly added a solution
  3. customprepared
  4. temperatureThe mixture was heated
  5. temperatureto reflux at 72° for ~42 hours
  6. additionwas added
  7. temperaturethe mixture refluxed for about an additional 5 hours
  8. customafter first removing 500 ml of ethanol
  9. extractionThe mixture was extracted twice with methylene chloride
  10. washwashed with water (an emulsion
  11. customformed
  12. dry with materialThe methylene chloride layer was dried over sodium sulfate
  13. additiontreated with activated charcoal
  14. filtrationfiltered
  15. customThe methylene chloride was removed by evaporation and 150 ml of methanol
  16. additionwas added
  17. temperatureThe mixture was chilled
  18. customthe 2,6-diethoxy-4-(trichloromethyl)pyridine product which precipitated
  19. customwas separated
  20. customThe product was recrystallized from 150 ml of methanol
  21. dry with materialdried over methylene chloride
  22. customThe product melted at 45.5°-47.0° C. and was recovered in a yield of 46 grams (32 percent of theoretical)

Sources & evidence

ORD record
ord-5ebcbea51f154988a29d2a4550406e43
Source dataset
uspto-grants-1980_02
Patent number
US04190662

Reaction notes

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