o-Xylyl bromide → HCID 23144544, compound

HRID 1967860Notes

Reaction equation

HRID 1967860 reaction equation
C[Si](C#N)(C)C.[CH:7](=[O:13])[C:8]1[O:12][CH:11]=[CH:10][CH:9]=1.C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[CH3:24][C:25]1[CH:32]=[CH:31][CH:30]=[CH:29][C:26]=1[CH2:27]Br.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[Cl-].[NH4+]>C1COCC1.[I-].[Zn+2].[I-]>[O:12]1[CH:11]=[CH:10][CH:9]=[C:8]1[C:7](=[O:13])[CH2:24][C:25]1[CH:32]=[CH:31][CH:30]=[CH:29][C:26]=1[CH3:27]

Participants

9

Reactant 6

HCID 6992o-Xylyl bromideHCID 7362FurfuralHCID 25517Ammonium ChlorideHCID 82115Trimethylsilyl cyanideHCID 2724141Tetrabutylammonium FluorideHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 23144544HCID 23144544, compoundYield 83.2%

Reagents, catalysts & solvents 2

HCID 9883512zinc(II)iodideCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

At 0° C., trimethylsilylcyanide (3.52 mL, 26.4 mmol) was added to a mixture of dried zinc iodide (100 mg) and furfural (1.99 mL, 24.0 mmol), followed by stirring at 0° C. for 30 minutes. THF (20 mL) was added to the reaction mixture, and at −78° C., a 1.0 mol/L solution of lithium hexamethyldisilazide in THF (24.0 mL, 24.0 mmol) was added dropwise thereto, followed by stirring at the same temperature for 15 minutes. A solution (10 mL) of 2-methylbenzyl bromide (2.68 mL, 20.0 mmol) in THF was added to the reaction mixture, followed by stirring at room temperature for 1 hour. 1.0 mol/L tetra(n-butyl)ammonium fluoride (26.4 mL, 26.4 mmol) was added to the reaction mixture, followed by stirring at room temperature for 30 minutes. A saturated aqueous solution of ammonium chloride was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed successively with a saturated aqueous solution of ammonium chloride and a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate, and then the solvent was distilled away under reduced pressure. The resulting residue was purified through silica gel column chromatography (hexane:ethyl acetate=4:1) to afford 1-(2-furyl)-2-(2-methylphenyl)ethanone (3.33 g, 83%).

Workup

  1. stirringby stirring at the same temperature for 15 minutes
  2. stirringby stirring at room temperature for 1 hour
  3. stirringby stirring at room temperature for 30 minutes
  4. extractionfollowed by extraction with ethyl acetate
  5. washThe organic layer was washed successively with a saturated aqueous solution of ammonium chloride
  6. dry with materiala saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate
  7. distillationthe solvent was distilled away under reduced pressure
  8. customThe resulting residue was purified through silica gel column chromatography (hexane:ethyl acetate=4:1)

Sources & evidence

ORD record
ord-e5b7b11817ba45119fad1052e334aa96
Source dataset
uspto-grants-2013_04
Patent number
US08420827B2

Reaction notes

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