2,7-Di-tert-butylfluorene → 1-(3-Butylcyclopentadien-1-yl)-1-(2,7-di-tert-butylfluoren-9-yl)-1,1-dimethylmethane

HRID 476290Notes

Reaction equation

HRID 476290 reaction equation
[C:1]([C:5]1[CH:17]=[CH:16][C:15]2[C:14]3[C:9](=[CH:10][C:11]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:12][CH:13]=3)[CH2:8][C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[Li][CH2:23][CH2:24][CH2:25][CH3:26]>CCOCC.CCCCCCC>[CH2:23]([C:24]1[CH:23]=[C:2]([C:1]([CH:8]2[C:7]3[CH:6]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:17]=[CH:16][C:15]=3[C:14]3[C:9]2=[CH:10][C:11]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:12][CH:13]=3)([CH3:4])[CH3:3])[CH2:26][CH:25]=1)[CH2:24][CH2:25][CH3:26]

Participants

5

Reactant 2

HCID 40900822,7-Di-tert-butylfluoreneHCID 178418339Butyllithium

Product 1

HCID 866291481-(3-Butylcyclopentadien-1-yl)-1-(2,7-di-tert-butylfluoren-9-yl)-1,1-dimethylmethaneYield 153.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8900HeptaneSolvent

Procedure

To 2,7-di-tert-butylfluorene (27.8 g, 100 mmol) dissolved in Et2O (200 mL) was added n-BuLi (11 mL of 10 M in hexanes, 110 mmol) at 0° C. The mixture was warmed to room temperature and stirred overnight. To the anion solution was added to 2-butyl-6,6-dimethylpentafulvene (F-2) (20 g, 123 mmol) at −78° C. in less than one minute. The mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and saturated NH4Cl aqueous solution. The mixture was extracted with Et2O. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent under vacuum gave a viscous oil. The oil was dissolved in heptane and purified through silica gel column with 5-10% CH2Cl2 in heptane. A mixture of isomers for the desired product (33.8 g, 76.8% yield) was obtained as a viscous oil.

Workup

  1. temperatureThe mixture was warmed to room temperature
  2. stirringstirred overnight
  3. customThe reaction was quenched with a mixture of ice and saturated NH4Cl aqueous solution
  4. extractionThe mixture was extracted with Et2O
  5. washThe organic layer was washed with water
  6. dry with materialdried over anhydrous sodium sulfate
  7. customRemoval of the solvent under vacuum
  8. customgave a viscous oil
  9. custompurified through silica gel column with 5-10% CH2Cl2 in heptane

Sources & evidence

ORD record
ord-0a2af88fa2ba42f9b0e2615f80bc9cb9
Source dataset
uspto-grants-2014_01
Patent number
US08637691B2

Reaction notes

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