Ammonium Chloride → 1-(4-Benzyloxyphenyl)-1-(4-methoxyphenyl)-2-phenylethene

HRID 2050948Notes

Reaction equation

HRID 2050948 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=O)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH4+].[Cl-]>BrC1C=CC(OC)=CC=1.C1COCC1.CCOCC>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C:15]([C:12]2[CH:13]=[CH:14][C:9]([O:8][CH3:1])=[CH:10][CH:11]=2)=[CH:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 12323407Benzyl 4-Benzyloxyphenyl Ketone

Product 1

HCID 544778771-(4-Benzyloxyphenyl)-1-(4-methoxyphenyl)-2-phenyletheneYield 159.6%

Reagents, catalysts & solvents 3

HCID 77304-BromoanisoleCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To the Grignard reagent prepared from 1.52 g (63 mg-atom) Mg turnings and 13.45 g (9 mL, 72 mmol) 4-bromoanisole (initiated with one I2 crystal and one drop EtBr2) in 25 mL THF was added 3 g (9.9 mmol) of Benzyl 4-benzyloxyphenyl ketone, prepared in Example 3. The reaction mixture was stirred at reflux for 48 h and then treated with 10 mL aqueous NH4Cl. After cooling to room temperature, the slurry was filtered, the filter cake washed with 50 mL THF, and the filtrates concentrated to give an orange oil. The oil was chromatographed over 60 g flash SiO2 (petroleum ether followed by Me2CO). The Me2CO fractions were combined, concentrated, dissolved in 100 mL 1:1 95% EtOH-2N H2SO4, and refluxed with stirring for 8 h. The solvents were removed to give a brown gum, which was dissolved in 100 mL Et2O, washed with saturated aqueous NaHCO3 (100 mL), brine (100 mL), and H2O (100 mL). The organic layer was dried (MgSO4), filtered, and concentrated to give a brown oil. The oil was purified on 60 g flash SiO2 (9:1 petroleum ether-CH2Cl2) to give 3.1 g of 1-(4-Benzyloxyphenyl)-1-(4-methoxyphenyl)-2-phenylethene (80%) as a clear oil. NMR δ7.41 (brs, 5H, O-benzyl C6H5), 7.3 to 6.75 (m, 9H, substituted rings' ArH and C=CH), 7.11 (s, 5H,=C--C6H5), 5.05 (s, 2H, OCH2Ph), 3.79 (s, 3H, OCH3).

Workup

  1. customprepared in Example 3
  2. temperatureat reflux for 48 h
  3. filtrationthe slurry was filtered
  4. washthe filter cake washed with 50 mL THF
  5. concentrationthe filtrates concentrated
  6. customto give an orange oil
  7. customThe oil was chromatographed over 60 g flash SiO2 (petroleum ether followed by Me2CO)
  8. concentrationconcentrated
  9. dissolutiondissolved in 100 mL 1:1 95% EtOH-2N H2SO4
  10. temperaturerefluxed
  11. stirringwith stirring for 8 h
  12. customThe solvents were removed
  13. customto give a brown gum, which
  14. washwashed with saturated aqueous NaHCO3 (100 mL), brine (100 mL), and H2O (100 mL)
  15. dry with materialThe organic layer was dried (MgSO4)
  16. filtrationfiltered
  17. concentrationconcentrated
  18. customto give a brown oil
  19. customThe oil was purified on 60 g flash SiO2 (9:1 petroleum ether-CH2Cl2)

Sources & evidence

ORD record
ord-03adb378632347319e9bbf1b59ed3dd6
Source dataset
uspto-grants-1991_05
Patent number
US05015666

Reaction notes

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