Hydrogen Peroxide → HCID 86690453, compound

HRID 2175728Notes

Reaction equation

HRID 2175728 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:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[OH:27]O>C1COCC1.II.O>[CH3:11][O:10][C:4]1[CH:3]=[C:2]([P:14](=[O:27])([C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 66180ChlorodiphenylphosphineHCID 6391871-Bromo-3,5-dimethoxybenzeneHCID 5462224Magnesium

Product 1

HCID 86690453HCID 86690453, compoundYield 97.5%

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 Schlenk flask (250 ml) with magnesium (1.2 g, 49.9 mmol), I2 (10 mg) and THF (40 ml). The mixture was reflux for 2 h. It was cooled to RT. The resulting light brown solution was transferred to another flask (250 ml) and it was cooled to −78° C. Chlorodiphenylphosphine (11 g, 49.9 mmol) in THF (30 ml) was added at −78° C. The mixture was stirred at −78° C. for 1 h, then it was slowly warmed up to RT and stirred at RT for 1 h. To the resulting reactions, water (50 ml) was added, then H2O2 (30%, 13 ml) was added dropwise at 0° C. The resulting mixture was stirred for 30 min. The organic layer was separated and the aqueous layer was extracted with ethyl acetate (50 ml×2). The combined organic layer was washed thoroughly with NaHSO3 (100 ml×3) and brine (100 ml×2) and dried over MgSO4. It was filtered and the solvent was removed to give a viscous oil which was purified with crystallization (CH2Cl2/Hexane=1:20) to give the product as a colorless solid (15.2 g, Yield: 97.5%). 1H NMR (300 Mhz, CD2Cl2) δ: 7.72-7.64 (m, 4H), 7.60-7.54 (m, 2H), 7.52-7.45 (m, 4H), 6.79 (dd, J1=2.1 Hz, 13.2 Hz, 2H), 6.64 (t, J=2.1 Hz, 1H), 3.77 (s, 6H). 31P NMR (121.5 MHz, CD2Cl2) δ: 29.03. 13C (75 MHz, CD2Cl2) δ: 161.18 (d, J=17.6 Hz), 135.17 (d, J=102 Hz), 132.99 (d, J=103 Hz), 132.12 (d, J=2.9 Hz), 132.11 (d, J=9.8 Hz), 109.87 (d, J=10.9 Hz), 103.91 (d, J=2.3 Hz), 55.74.

Workup

  1. temperatureThe mixture was reflux for 2 h
  2. customThe resulting light brown solution was transferred to another flask
  3. temperature(250 ml) and it was cooled to −78° C
  4. temperatureit was slowly warmed up to RT
  5. stirringstirred at RT for 1 h
  6. stirringThe resulting mixture was stirred for 30 min
  7. customThe organic layer was separated
  8. extractionthe aqueous layer was extracted with ethyl acetate (50 ml×2)
  9. washThe combined organic layer was washed thoroughly with NaHSO3 (100 ml×3) and brine (100 ml×2)
  10. dry with materialdried over MgSO4
  11. filtrationIt was filtered
  12. customthe solvent was removed
  13. customto give a viscous oil which
  14. customwas purified with crystallization (CH2Cl2/Hexane=1:20)

Sources & evidence

ORD record
ord-b03b6bcdc8484082925368099e5bc075
Source dataset
uspto-grants-2015_06
Patent number
US09062085B2

Reaction notes

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