Methyl iodide → 2,7-Dibromo-9-methyl-9H-fluorene

HRID 1810812Notes

Reaction equation

HRID 1810812 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.[CH2:16]([Li])CCC.CI.ClCCl>C1COCC1.O>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[CH:5]([CH3:16])[C:4]=2[CH:3]=1

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 6344DichloromethaneHCID 1400732,7-DibromofluoreneHCID 178418339Butyllithium

Product 1

HCID 125898062,7-Dibromo-9-methyl-9H-fluoreneYield 70.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

2,7-dibromofluorene (30 g, 92.59 mmol) was dissolved in anhydrous THF (300 mL) under nitrogen and cooled to −78° C. To solution at −78° C., added n-butyllithium (40.36 mL, 100.9 mmol) over 5 minutes and allowed reaction stir for another 10 minutes. To reaction, then add methyl iodide (6.29 mL, 100.9 mmol) and allowed reaction to stir at −78° C. for 2.0 hours. The reaction was poured into a mixture of dichloromethane and water. The organic layer was collected, and the water layer was further extracted with dichloromethane. Combined all organic layers and removed solvent via vacuo. The crude material was triturated with hexanes and filtered using Buchner funnel to give white solids (22 g, 70%).1H NMR (500 MHz, CDCl3): δ=7.62 (s, 2H), 7.56-7.58 (d, 2H), 7.48-7.50 (dd, 2H), 3.90-3.94 (q, 1H), 1.49-1.51 (d, 3H).

Workup

  1. customreaction
  2. customTo reaction
  3. customreaction
  4. stirringto stir at −78° C. for 2.0 hours
  5. customThe organic layer was collected
  6. extractionthe water layer was further extracted with dichloromethane
  7. customremoved solvent via vacuo
  8. customThe crude material was triturated with hexanes
  9. filtrationfiltered

Sources & evidence

ORD record
ord-70154fed68434283b8893ca80c407809
Source dataset
uspto-grants-2013_01
Patent number
US08362193B2

Reaction notes

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