Dimethylformamide → Dibenzyl ether

HRID 2369467Notes

Reaction equation

HRID 2369467 reaction equation
CN([CH:4]=[O:5])C.[H-].[Na+].[CH:8]1[CH:13]=[CH:12][C:11]([CH2:14]Br)=[CH:10][CH:9]=1.[NH4+].[Cl-]>C1COCC1.CCCC[N+](CCCC)(CCCC)CCCC.[I-].CCOCC>[CH2:14]([O:5][CH2:4][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:11]1[CH:12]=[CH:13][CH:8]=[CH:9][CH:10]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 25517Ammonium Chloride

Product 1

HCID 7657Dibenzyl ether

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Methyl glycoside alcohol 20 (160 mg, 0.32 mmol) was dissolved in THF (0.32 M, 1.0 mL). Then DMF (0.10 mL) was added as a co-solvent. The solution was cooled to 0° C., and NaH (60% dispersion in mineral oil, 19 mg, 0.48 mmol) was added all at once and stirred for 20 minutes. BnBr (0.060 mL, 0.48 mmol) was then added all at once, followed by the addition of TBAI (10 mg). The reaction was allowed to warm to r.t. and stirred overnight. After diluting with Et2O (20 mL), a saturated solution of NH4Cl (10 mL) was slowly added to quench the reaction. The aqueous layer was extracted with EtOAc (2×10 mL). The organic extracts were combined and dried with MgSO4. After filtration and evaporation of the volatiles under reduced pressure, chromatography (20:1→4:1 hexanes:EtOAc) gave benzyl ether I as a colorless oil (160 mg, 84%).

Workup

  1. temperatureto warm to r.t.
  2. stirringstirred overnight
  3. customto quench
  4. customthe reaction
  5. extractionThe aqueous layer was extracted with EtOAc (2×10 mL)
  6. dry with materialdried with MgSO4
  7. filtrationAfter filtration and evaporation of the volatiles under reduced pressure, chromatography (20:1→4:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-fdfac99a19ef47faade75eb13c065fd1
Source dataset
uspto-grants-2014_04
Patent number
US08703977B2

Reaction notes

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