4,4'-Bis(dimethylamino)benzophenone → 1,1-Bis(4-dimethylaminophenyl)propene

HRID 1282455Notes

Reaction equation

HRID 1282455 reaction equation
[CH2:1]([Mg]Br)[CH3:2].[CH3:5][N:6]([CH3:24])[C:7]1[CH:23]=[CH:22][C:10]([C:11]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][CH:14]=2)=O)=[CH:9][CH:8]=1.[Cl-].[NH4+]>C1COCC1>[CH3:5][N:6]([CH3:24])[C:7]1[CH:23]=[CH:22][C:10]([C:11]([C:13]2[CH:18]=[CH:17][C:16]([N:19]([CH3:21])[CH3:20])=[CH:15][CH:14]=2)=[CH:1][CH3:2])=[CH:9][CH:8]=1

Participants

5

Reactant 3

HCID 70314,4'-Bis(dimethylamino)benzophenoneHCID 25517Ammonium ChlorideHCID 178418443HCID 178418443, compound

Product 1

HCID 2358411,1-Bis(4-dimethylaminophenyl)propeneYield 65.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Into a reactor was introduced 102 mL (82.0 mmol; 0.80 M THF solution) of ethylmagnesium bromide under a nitrogen atmosphere. The contents were cooled to 0° C. Thereto was gradually added dropwise a solution prepared by mixing 20.0 g (74.5 mmol) of 4,4′-bis(dimethylamino)benzophenone and 40 mL of THF. This mixture was stirred at room temperature for 5 hours. Saturated aqueous ammonium chloride solution was added to the resultant reaction mixture, and the metal salt yielded was removed by Celite filtration. The organic layer was separated from the filtrate and then extracted with toluene. Thereafter, the solvent was removed under reduced pressure. The concentrate was dissolved in 150 mL of toluene, and 0.1 g of p-toluenesulfonic acid monohydrate was added thereto. Azeotropic dehydration was conducted with toluene refluxing. After being cooled, the reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, subsequently dried with anhydrous magnesium sulfate, and then concentrated under reduced pressure. This concentrate was purified by column chromatography to obtain 13.6 g (65%) of light-yellow crystals. 1H-NMR (CDCl3) δ 1.77 (d, J=7.0 Hz, 3H), 2.92 (s, 6H), 2.98 (s, 6H), 5.94 (q, J=7.0 Hz, 1H), 6.58-6.79 (m, 4H), 7.02-7.18 (m, 4H).

Workup

  1. additionThereto was gradually added dropwise a solution
  2. customprepared
  3. customreaction mixture
  4. customthe metal salt yielded
  5. customwas removed by Celite filtration
  6. customThe organic layer was separated from the filtrate
  7. extractionextracted with toluene
  8. customThereafter, the solvent was removed under reduced pressure
  9. dissolutionThe concentrate was dissolved in 150 mL of toluene
  10. addition0.1 g of p-toluenesulfonic acid monohydrate was added
  11. temperatureAfter being cooled
  12. washthe reaction mixture was washed with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution
  13. dry with materialsubsequently dried with anhydrous magnesium sulfate
  14. concentrationconcentrated under reduced pressure
  15. customThis concentrate was purified by column chromatography

Sources & evidence

ORD record
ord-a024d2c3fb6a44249268d293667b050d
Source dataset
uspto-grants-2002_09
Patent number
US06455720B1

Reaction notes

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