Hydrogen Peroxide → HCID 86690455, compound

HRID 2175732Notes

Reaction equation

HRID 2175732 reaction equation
Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[C:4]([O:10][CH3:11])[CH:3]=1.[Mg].Cl[P:14]([C:25]1[CH:30]=[C:29]([CH3:31])[C:28]([O:32][CH3:33])=[C:27]([CH3:34])[CH:26]=1)[C:15]1[CH:20]=[C:19]([CH3:21])[C:18]([O:22][CH3:23])=[C:17]([CH3:24])[CH:16]=1.[OH:35]O>C1COCC1.II.O>[CH3:11][O:10][C:4]1[CH:3]=[C:2]([P:14](=[O:35])([C:25]2[CH:30]=[C:29]([CH3:31])[C:28]([O:32][CH3:33])=[C:27]([CH3:34])[CH:26]=2)[C:15]2[CH:20]=[C:19]([CH3:21])[C:18]([O:22][CH3:23])=[C:17]([CH3:24])[CH:16]=2)[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 6391871-Bromo-3,5-dimethoxybenzeneHCID 4368797BIS(3,5-DIMETHYL-4-METHOXYPHENYL)CHLOROPHOSPHINEHCID 5462224Magnesium

Product 1

HCID 86690455HCID 86690455, compound

Reagents, catalysts & solvents 3

HCID 807IodineCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

1-Bromo-3,5-dimethoxybenzene (10 g, 46.1 mmol) in THF (60 ml) was added to a flask (250 ml) with magnesium (1.2 g, 49.9 mmol) and I2 (20 mg) in THF (40 ml) at 60° C. The mixture was refluxed for 2 h after the addition was completed. It was cooled to RT. The resulting light brown solution was transferred to another flask (250 ml). It was cooled to −78° C. and chlorobis(4-methoxy-3,5-dimethylphenyl)phosphine (16.8 g, 49.9 mmol) in THF (40 ml) was added dropwise at −78° C. within 1 h. The resulting mixture was stirred at −78° C. for 0.5 h, then slowly warmed up to RT and stirred at RT for 30 min. To the resulting mixture water (50 ml) was added, then H2O2 (13 ml) was added dropwise at 0° C. The mixture was stirred for 0.5 h at RT. The organic layer was separated and the aqueous layer was extracted with ethyl acetate (100 ml×2) and CH2Cl2 (100 ml×1). The combined organic layer was washed with brine (200 ml×2), NaHSO3 (200 ml×3) and dried over MgSO4. It was filtered and the solvent was removed. The viscous residues were stirred with CH2Cl2/hexane (5 ml/100 ml) for 1 h. The solid was collected by filtration to give the product as a colorless solid (17.4 g, 83 yield). 1H NMR (300 MHz, CD2Cl2) δ: 7.32 (s, 2H), 7.28 (s, 2H), 6.76 (dd, J=2.4 Hz, J=12.9 Hz, 2H), 6.61 (t, J=2.4 Hz, 1H), 3.78 (s, 6H), 3.75 (s, 6H), 2.28 (s, 12H). 31P NMR (121.5 MHz, CD2Cl2) δ: 28.4.

Workup

  1. temperatureThe mixture was refluxed for 2 h
  2. additionafter the addition
  3. customThe resulting light brown solution was transferred to another flask
  4. temperatureIt was cooled to −78° C.
  5. temperatureslowly warmed up to RT
  6. stirringstirred at RT for 30 min
  7. stirringThe mixture was stirred for 0.5 h at RT
  8. customThe organic layer was separated
  9. extractionthe aqueous layer was extracted with ethyl acetate (100 ml×2) and CH2Cl2 (100 ml×1)
  10. washThe combined organic layer was washed with brine (200 ml×2), NaHSO3 (200 ml×3)
  11. dry with materialdried over MgSO4
  12. filtrationIt was filtered
  13. customthe solvent was removed
  14. stirringThe viscous residues were stirred with CH2Cl2/hexane (5 ml/100 ml) for 1 h
  15. filtrationThe solid was collected by filtration

Sources & evidence

ORD record
ord-a08a037ea04c450193a1539504eafdd3
Source dataset
uspto-grants-2015_06
Patent number
US09062085B2

Reaction notes

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