Hydrochloric Acid → 9-Methylfluorene

HRID 2416363Notes

Reaction equation

HRID 2416363 reaction equation
[CH:1]1[C:13]2[CH2:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[Li][CH2:15]CCC.CI.Cl>C1COCC1>[CH3:15][CH:12]1[C:11]2[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=2[C:5]2[C:13]1=[CH:1][CH:2]=[CH:3][CH:4]=2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6328Methyl iodideHCID 6853FluoreneHCID 178418339Butyllithium

Product 1

HCID 172999-MethylfluoreneYield 67.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

A mixture of fluorene (78.3 g) and THF (700 mL) was cooled down to −70° C., and n-BuLi (300 mL, corresponding to 0.48 mol) was dropwise added thereto while maintaining −60° C. or lower. Then, methyl iodide (66.8 g) was added, and the temperature was allowed to slowly go back to a room temperature. The mixture was cooled again down to 0° C. to add 3M-hydrochloric acid (300 mL), and the reaction mixture was extracted with toluene. The organic layer obtained was washed well in order with saturated sodium hydrogencarbonate, saturated sodium hydrogensulfite and water, and then dried on anhydrous magnesium sulfate. The solvent was distilled off from this organic layer under reduced pressure, and the residue was purified by means of column chromatography (silica gel, eluting solvent: toluene/heptane [40/60]) and recrystallization (ethanol) to obtain 9-methylfluorene (57.4 g) of pale yellow crystal. Melting point: 47.3-48.8° C.

Workup

  1. temperaturewhile maintaining −60° C.
  2. customto slowly go back to a room temperature
  3. temperatureThe mixture was cooled again down to 0° C.
  4. extractionthe reaction mixture was extracted with toluene
  5. customThe organic layer obtained
  6. washwas washed well in order with saturated sodium hydrogencarbonate, saturated sodium hydrogensulfite and water
  7. dry with materialdried on anhydrous magnesium sulfate
  8. distillationThe solvent was distilled off from this organic layer under reduced pressure
  9. customthe residue was purified by means of column chromatography (silica gel, eluting solvent: toluene/heptane [40/60]) and recrystallization (ethanol)

Sources & evidence

ORD record
ord-3de1aef0ca9e4a07a7c579ccc84ac632
Source dataset
uspto-grants-2004_11
Patent number
US06824709B2

Reaction notes

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