Benzyl Bromide → HCID 86653775, compound

HRID 1021202Notes

Reaction equation

HRID 1021202 reaction equation
[CH3:1][C:2]1[C:7]([CH3:8])=[C:6](O)[C:5]([CH3:10])=[CH:4][C:3]=1[OH:11].[CH2:12](Br)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[C:20]([O-:23])([O-])=O.[K+].[K+]>CN(C=O)C>[CH2:12]([O:11][C:3]1[C:2]([CH3:1])=[C:7]([CH3:8])[C:6]([O:23][CH2:20][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:5]([CH3:10])[CH:4]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 7498Benzyl Bromide2×HCID 11430Potassium Carbonate2×HCID 12785Trimethylhydroquinone

Product 1

HCID 86653775HCID 86653775, compoundYield 161.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 2,3,5-trimethylbenzene-1,4-diol (15.2 g, 100 mmol) in DMF (150 mL) was treated with benzyl bromide (35.7 mL, 51.6 g, 300 mmol, 3 equiv.) and anhydrous K2CO3 (55.3 g, 400 mmol, 4 equiv.). The brown suspension was heated to 60° C. for 48 h at which time the reaction was judged incomplete by HPLC. Additional benzyl bromide (37 mL, 300 mmol, 3 equiv.) and K2CO3 (50 g, 362 mmol, 3.6 equiv.) were added and heated to 60° C. for an additional 48 h. The reaction was cooled, filtered through Celite, the filter cake rinsed 2×100 mL ethyl acetate and the combined filtrates washed with 500 mL H2O. The aqueous layer was extracted 4×250 mL ethylacetate and concentrated at 80° C. by rotary evaporation. The brown residue was poured onto 300 mL water which precipitated a light brown solid and the resulting suspension stirred overnight. The brown solid was collected by filtration, washed with 2×50 mL H2O and dried, yielding 26.8 g of 2,5-bis(benzyloxy)-3,4,6-trimethylbenzene as a brown solid. 1H NMR (400 MHz, CDCl3) δ=7.50-7.34 (m, 10 H), 6.64 (s, 1 H), 5.03 (s, 2 H), 4.74 (s, 2 H), 2.30 (s, 3 H), 2.25 (s, 3 H), 2.20 (s, 3 H) ppm.

Workup

  1. temperatureheated to 60° C. for an additional 48 h
  2. temperatureThe reaction was cooled
  3. filtrationfiltered through Celite
  4. washthe filter cake rinsed 2×100 mL ethyl acetate
  5. washthe combined filtrates washed with 500 mL H2O
  6. extractionThe aqueous layer was extracted 4×250 mL ethylacetate
  7. concentrationconcentrated at 80° C. by rotary evaporation
  8. additionThe brown residue was poured onto 300 mL water which
  9. customprecipitated a light brown solid
  10. filtrationThe brown solid was collected by filtration
  11. washwashed with 2×50 mL H2O
  12. customdried

Sources & evidence

ORD record
ord-42207f5024df49c8a9f32b463a8a1b3e
Source dataset
uspto-grants-2014_05
Patent number
US08716527B2

Reaction notes

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