4-Bromophenol → trans-4-(4-Bromophenoxy)tetrahydrofuran-3-ol

HRID 2060825Notes

Reaction equation

HRID 2060825 reaction equation
[CH:1]12[O:6][CH:5]1[CH2:4][O:3][CH2:2]2.[Br:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.O1CCOCC1.C(OCC)(=O)C>[Br:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][C@@H:5]2[CH2:4][O:3][CH2:2][C@H:1]2[OH:6])=[CH:10][CH:9]=1

Participants

7

Reactant 3

HCID 78084-BromophenolHCID 10796Cesium carbonateHCID 675113,6-Dioxabicyclo[3.1.0]hexane

Product 1

HCID 67195067trans-4-(4-Bromophenoxy)tetrahydrofuran-3-ol

Reagents, catalysts & solvents 3

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

3,6-Dioxabicyclo[3.1.0]hexane (100 g, 1.16 mol), 4-bromophenol (241.1 g, 1.39 mol), cesium carbonate (492 g, 1.51 mol) and benzyltriethylammonium chloride (52.9 g, 0.23 mol) were suspended in dioxane (1 L) and heated at reflux for 18 hours. The reaction was cooled to room temperature and diluted with ethyl acetate, then washed with saturated aqueous sodium carbonate solution. The aqueous layer was extracted with ethyl acetate, and the combined organic portions were dried over sodium sulfate, filtered and concentrated in vacuo, to provide crude product, which solidified on standing. This was used without purification in the next step. Yield: 354 g, >100%, assumed quantitative. Material from a smaller-scale experiment carried out in similar fashion was purified by silica gel chromatography for characterization (Gradient: 10% to 35% ethyl acetate in heptane), to afford trans-4-(4-bromophenoxy)tetrahydrofuran-3-ol as a solid.

Workup

  1. temperatureheated
  2. temperatureat reflux for 18 hours
  3. washwashed with saturated aqueous sodium carbonate solution
  4. extractionThe aqueous layer was extracted with ethyl acetate
  5. dry with materialthe combined organic portions were dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto provide crude product, which
  9. customThis was used without purification in the next step
  10. customwas purified by silica gel chromatography for characterization (Gradient: 10% to 35% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-e7478cf45e754f7eb2a731801a468d49
Source dataset
uspto-grants-2012_10
Patent number
US08278457B2

Reaction notes

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