Benzyl Bromide → HCID 67523754, compound

HRID 1424370Notes

Reaction equation

HRID 1424370 reaction equation
[OH:1][C:2]1[C:11]2[C:10](=[O:12])[O:9][C:8]([CH3:14])([CH3:13])[O:7][C:6]=2[CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+].[CH2:21](Br)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>CN(C)C=O>[CH2:21]([O:1][C:2]1[C:11]2[C:10](=[O:12])[O:9][C:8]([CH3:14])([CH3:13])[O:7][C:6]=2[CH:5]=[CH:4][CH:3]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 110525144H-1,3-Benzodioxin-4-one, 5-hydroxy-2,2-dimethyl-

Product 1

HCID 67523754HCID 67523754, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 5-hydroxy-2,2-dimethyl-4H-benzo[d][1,3]dioxin-4-one (6.00 g, 30.9 mmol) (Hadfield, A. et al., Synthetic Communications, 24(7):1025-1028 (1994)) in N,N-dimethylformamide (35 mL) was treated with powdered anhydrous potassium carbonate (5.15 g, 37.26 mmol) added all at once. The resulting mixture was stirred in vacuo for 10 min. and then flushed with nitrogen. The reaction flask was placed in a water bath (22° C.) and treated with benzyl bromide (5.55 g, 32.16 mmol) added dropwise over 15 min. The resulting mixture was then stirred at 22° C. for 18 h. The solid formed was filtered and washed with N,N-dimethylformamide. The filtrate was evaporated in vacuo and the residual oil was diluted with ethyl acetate (300 mL), washed with cold 0.1 N hydrochloric acid, saturated sodium bicarbonate and brine. After drying over anhydrous magnesium sulfate, evaporation of the solvent gave a thick syrup. Chromatography on silica gel (4×13 cm, elution toluene-ethyl acetate 0-5%) gave 8.78 g (100% yield) of the title material as a white solid. LC (Method A): 1.982 min. 1H NMR (CDCl3, 600 MHz) δ ppm: 1.69 (s, 6H), 5.23 (s, 2H), 6.53 (d, J=8.2 Hz, 1H), 6.62 (d, J=8.4 Hz, 1H), 7.24-7.3 (m, 1H), 7.34-7.4 (m, 3H), 7.52 (broad d, J=7.4 Hz 2H).

Workup

  1. additionadded all at once
  2. customflushed with nitrogen
  3. customThe reaction flask was placed in a water bath
  4. additionadded dropwise over 15 min
  5. stirringThe resulting mixture was then stirred at 22° C. for 18 h
  6. customThe solid formed
  7. filtrationwas filtered
  8. washwashed with N,N-dimethylformamide
  9. customThe filtrate was evaporated in vacuo
  10. additionthe residual oil was diluted with ethyl acetate (300 mL)
  11. washwashed with cold 0.1 N hydrochloric acid, saturated sodium bicarbonate and brine
  12. dry with materialAfter drying over anhydrous magnesium sulfate, evaporation of the solvent
  13. customgave a thick syrup

Sources & evidence

ORD record
ord-a64cfec88cd847dca6aa1599a3cd0eb1
Source dataset
uspto-grants-2015_01
Patent number
US08927688B2

Reaction notes

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