Tetrahydrofuran → HCID 19088022, compound

HRID 1464531Notes

Reaction equation

HRID 1464531 reaction equation
[CH2:1]1[CH2:5][O:4][CH2:3][CH2:2]1.Br[C:7]1[C:12]([CH3:13])=[C:11]([O:14][CH3:15])[C:10]([CH3:16])=[C:9]([CH3:17])[C:8]=1[O:18][CH3:19].C([Li])CCC.C(Br)C=CC>O>[CH3:13][C:12]1[CH2:7][C:8]([CH:1]([CH3:5])[CH2:2][CH2:3][OH:4])([O:18][CH3:19])[C:9]([CH3:17])=[C:10]([CH3:16])[C:11]=1[O:14][CH3:15]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 1224142-Butene, 1-bromo-HCID 2973651-Bromo-2,5-dimethoxy-3,4,6-trimethylbenzeneHCID 178418339Butyllithium

Product 1

HCID 19088022HCID 19088022, compoundYield 30%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
-70 °C

Procedure

A THF solution (50 ml) of 2-bromo-3,5,6-trimethyl-1,4-dimethoxybenzene (10 g, 40 mmole) was cooled to -70° C. under an atmosphere of argon, and n-butyllithium (20%, hexane solution) was added dropwise to the solution, followed by stirring at -70° C. for 10 minutes. Subsequently, cuprous bromide (5.70 g, 40 mmole) was added to the mixed solution, and the temperature of the reaction solution was raised to 0° C. The reaction solution was cooled again to -70° C., and crotyl bromide (5.4 g, 40 mmole) was added. Stirring was effected until the reaction solution reached the room temperature, and the reaction was suspended by adding 100 ml of water. The reaction solution was extracted with IPE, and the organic layer was washed with water, dried and concentrated under reduced pressure. The residue was dissolved in THF (50 ml), and sodium boron hydride (1 g) was added to the solution. Boron trifluoride etherate (1.5 ml) was added dropwise to the reaction solution, and after stirring was effected for 1 hour and 50 ml of water was added, 3N aqueous potassium hydroxide solution (50 ml) was added dropwise to the mixed solution. 30% Aqueous hydrogen peroxide solution was added to the reaction solution under cooling, followed by stirring under the same conditions for 18 hours. The reaction solution was extracted with IPE, and the organic layer was washed with water, dried and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluting solution: IPE) to give 3-(3,5,6-trimethyl-1,4-dimethoxyphenyl)-butan-1-ol (3 g, 30%).

Workup

  1. temperaturethe temperature of the reaction solution was raised to 0° C
  2. temperatureThe reaction solution was cooled again to -70° C.
  3. stirringStirring
  4. customthe room temperature
  5. extractionThe reaction solution was extracted with IPE
  6. washthe organic layer was washed with water
  7. customdried
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThe residue was dissolved in THF (50 ml)
  10. additionsodium boron hydride (1 g) was added to the solution
  11. additionBoron trifluoride etherate (1.5 ml) was added dropwise to the reaction solution
  12. stirringafter stirring
  13. waitwas effected for 1 hour
  14. addition50 ml of water was added
  15. addition3N aqueous potassium hydroxide solution (50 ml) was added dropwise to the mixed solution
  16. addition30% Aqueous hydrogen peroxide solution was added to the reaction solution
  17. temperatureunder cooling
  18. stirringby stirring under the same conditions for 18 hours
  19. extractionThe reaction solution was extracted with IPE
  20. washthe organic layer was washed with water
  21. customdried
  22. concentrationconcentrated under reduced pressure
  23. customThe residue was purified by silica gel column chromatography (eluting solution: IPE)

Sources & evidence

ORD record
ord-f71546e5dec541468b1a4f386c665125
Source dataset
uspto-grants-1994_04
Patent number
US05304658

Reaction notes

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