Iodine → HCID 53861937, compound

HRID 2050949Notes

Reaction equation

HRID 2050949 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.II.[C:18]1([C:26]([CH2:28][C:29]2[CH:36]=[CH:35][C:32]([O:33][CH3:34])=[CH:31][CH:30]=2)=O)[CH:25]=[CH:24][C:21]([O:22][CH3:23])=[CH:20][CH:19]=1.OS(O)(=O)=O>C1COCC1>[CH2:9]([O:8][C:5]1[CH:6]=[CH:7][C:2]([C:28]([C:29]2[CH:36]=[CH:35][C:32]([O:33][CH3:34])=[CH:31][CH:30]=2)=[CH:26][C:18]2[CH:19]=[CH:20][C:21]([O:22][CH3:23])=[CH:24][CH:25]=2)=[CH:3][CH:4]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 807IodineHCID 1118Sulfuric AcidHCID 67120DesoxyanisoinHCID 1388351-Bromo-4-phenylmethoxybenzene

Product 1

HCID 53861937HCID 53861937, compoundYield 99.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Benzyl 4-bromophenyl ether (13.155 g; 50 mmol), prepared in Example 2, in 20 mL THF was added to Mg turnings (1.17 g; 48 mg-atom) in 20 mL THF. Grignard reagent formation was facilitated by addition of a few drops of EtBr2, one crystal of I2, and heat. This mixture was stirred and heated to reflux for 2 h. 11.54 g (45 mmol) desoxyanisoin was added under reflux as a slurry in 60 mL THF. The resulting mixture was stirred at reflux for 18 h, cooled to room temperature, poured onto 200 g 2N H2SO4 and ice (1:1), and stirred at room temperature until the ice melted. The resulting mixture was placed in a separatory funnel and extracted with 200 mL Et2O. The organic layer was washed with aqueous Na2SO5 (100 mL), and brine (2×100 mL). The combined aqueous layers were extracted with Et2O (50 mL). The combined organic layers were dried (MgSO4), filtered, and concentrated to give 19 g of a wine colored oil, which was dissolved in Et2O and refrigerated to precipitate any unreacted deoxyanisoin. After filtration and concentration of the solution, the resulting oil was purified on 60 g flash SiO2 (7:3 petroleum ether-CH2Cl2) to yield 12.4 g (65%) of 1-(4-Benzyloxyphenyl)-2,2-bis(4-methoxyphenyl)ethene as a yellow oil. NMR δ7.41 (s, 5H, O-benzyl C6H5), 7.35 to 6.57 (m, 13H, ArH and C=CH), 5.07 (s, 2H, PhCH2O), 3.78 (s, 1.5H, geminal ring OCH3), 3.77 (s, 1.5H, central ring OCH3), 3.72 (s, 3H, vicinal ring OCH3).

Workup

  1. temperatureheat
  2. temperatureheated
  3. temperatureto reflux for 2 h
  4. stirringThe resulting mixture was stirred
  5. temperatureat reflux for 18 h
  6. customThe resulting mixture was placed in a separatory funnel
  7. extractionextracted with 200 mL Et2O
  8. washThe organic layer was washed with aqueous Na2SO5 (100 mL), and brine (2×100 mL)
  9. extractionThe combined aqueous layers were extracted with Et2O (50 mL)
  10. dry with materialThe combined organic layers were dried (MgSO4)
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-05f03bd2639d49b6bf48b80225598a56
Source dataset
uspto-grants-1991_05
Patent number
US05015666

Reaction notes

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