Glycidol → HCID 86650541, compound

HRID 2066637Notes

Reaction equation

HRID 2066637 reaction equation
[CH2:1]1[O:3][CH:2]1[CH2:4][OH:5].[F:6][C:7]([F:18])([F:17])[O:8][C:9]1[CH:16]=[CH:15][C:12]([CH2:13]Br)=[CH:11][CH:10]=1.[H-].[Na+]>CN(C=O)C>[F:6][C:7]([F:17])([F:18])[O:8][C:9]1[CH:16]=[CH:15][C:12]([CH2:13][O:5][CH2:4][CH:2]2[CH2:1][O:3]2)=[CH:11][CH:10]=1

Participants

5

Reactant 3

HCID 11164GlycidolHCID 24758Sodium hydrideHCID 1427851-(Bromomethyl)-4-(trifluoromethoxy)benzene

Product 1

HCID 86650541HCID 86650541, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of glycidol (115) (303 mg, 4.09 mmol) and 4-(trifluoromethoxy)benzyl bromide (0.810 mL, 5.06 mmol) in anhydrous DMF (6 mL) under N2 at 0° C. was treated with 60% NaH (246 mg, 6.15 mmol), then quickly degassed and resealed under N2. After stirring at room temperature for 7 h, the mixture was cooled (CO2/acetone), quenched with ice/aqueous NaHCO3 (20 mL), added to water (100 mL) and extracted with EtOAc (4×100 mL). The extracts were washed with brine (100 mL) and evaporated to dryness and the residue was chromatographed on silica gel. Elution with 0-5% Et2O/petroleum ether firstly gave foreruns, and then further elution with 5-10% Et2O/petroleum ether gave 2-({[4-(trifluoromethoxy)benzyl]oxy}methyl)oxirane (116) (625 mg, 62%) as an oil; 1H NMR (CDCl3) δ 7.38 (dt, J=8.7, 2.3 Hz, 2H), 7.20 (br dd, J=8.7, 0.7 Hz, 2H), 4.62 (d, J=12.0 Hz, 1H), 4.56 (d, J=12.0 Hz, 1H), 3.82 (dd, J=11.5, 2.8 Hz, 1H), 3.43 (dd, J=11.5, 6.0 Hz, 1H), 3.21 (m, 1H), 2.82 (dd, J=4.9, 4.2 Hz, 1H), 2.63 (dd, J=5.0, 2.7 Hz, 1H); HRESIMS calcd for C11H11F3NaO3 m/z [M+Na]+ 271.0552. found 271.0557.

Workup

  1. customquickly degassed
  2. temperaturethe mixture was cooled (CO2/acetone)
  3. customquenched with ice/aqueous NaHCO3 (20 mL)
  4. additionadded to water (100 mL)
  5. extractionextracted with EtOAc (4×100 mL)
  6. washThe extracts were washed with brine (100 mL)
  7. customevaporated to dryness
  8. customthe residue was chromatographed on silica gel
  9. washElution with 0-5% Et2O/petroleum ether firstly gave foreruns
  10. washfurther elution with 5-10% Et2O/petroleum ether

Sources & evidence

ORD record
ord-a3e136e155244f1580c1f7f53c942a9e
Source dataset
uspto-grants-2012_10
Patent number
US08293734B2

Reaction notes

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