Dimethylformamide → 2-(p-Methoxyphenoxy)-3-(dimethylamino)acrolein

HRID 1179671Notes

Reaction equation

HRID 1179671 reaction equation
P(Cl)(Cl)(Cl)=O.[CH3:6][N:7]([CH3:10])[CH:8]=O.C([O:13][CH:14](OCC)[CH2:15][O:16][C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=1)C.C(=O)([O-])[O-].[K+].[K+]>O.C(OCC)(=O)C.C(Cl)(Cl)Cl>[CH3:6][N:7]([CH3:10])[CH:8]=[C:15]([O:16][C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=1)[CH:14]=[O:13]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 24813Phosphorus oxychlorideHCID 2513151-(2,2-Diethoxyethoxy)-4-methoxybenzene

Product 1

HCID 544980242-(p-Methoxyphenoxy)-3-(dimethylamino)acroleinYield 44%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

Phosphorus oxychloride (18.4 g, 120 mmol) was added to dimethylformamide (8.8 g, 120 mmol), maintaining the temperature below 25° C. by an external ice-bath. Upon completion of the addition the reaction mixture was heated to 50° C. for 45 minutes and then cooled to room temperature. Chloroform (35 ml) was added and the resulting solution was brought to reflux. 4-Methoxyphenoxyacetaldehyde diethylacetal (9.61 g, 40.0 mmol) was added in portions. After heating for 3 hours at reflux the solution was cooled to room temperature and poured carefully onto a solution of potassium carbonate (115 g) in water (100 ml). The mixture was cooled in an ice-bath to around room temperature and extracted twice with dichloromethane. The combined organic layers were dried over sodium sulphate, filtered and evaporated in vacuo yielding a brown oil. The residue was heated with ethyl acetate:heptane and decanted, leaving a brown oil. The solvent was removed in vacuo to give a brown oil, which was purified by flash column chromatography (SiO2, ethyl acetate) yielding the title compound (3.87 g, 44% yield) as a white solid.

Workup

  1. temperaturemaintaining the temperature below 25° C. by an external ice-bath
  2. additionUpon completion of the addition the reaction mixture
  3. temperaturecooled to room temperature
  4. temperatureto reflux
  5. temperatureAfter heating for 3 hours
  6. temperatureat reflux the solution
  7. temperaturewas cooled to room temperature
  8. temperatureThe mixture was cooled in an ice-bath to around room temperature
  9. extractionextracted twice with dichloromethane
  10. dry with materialThe combined organic layers were dried over sodium sulphate
  11. filtrationfiltered
  12. customevaporated in vacuo
  13. customyielding a brown oil
  14. customheptane and decanted
  15. customleaving a brown oil
  16. customThe solvent was removed in vacuo
  17. customto give a brown oil, which
  18. customwas purified by flash column chromatography (SiO2, ethyl acetate)

Sources & evidence

ORD record
ord-4e06b60a2f374fd4a084663af8b0537a
Source dataset
uspto-grants-2007_10
Patent number
US07279470B2

Reaction notes

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