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

HRID 476289Notes

Reaction equation

HRID 476289 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:23]([C:24]([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)([C:5]2[CH:17]=[CH:16][CH:15]=[CH:7][CH:6]=2)[C:25]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:26]=2)[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 866291471-(3-Butylcyclopentadien-1-yl)-1-(2,7-di-tert-butylfluoren-9-yl)-1,1-diphenylmethaneYield 171.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8900HeptaneSolvent

Procedure

To 2,7-di-tert-butylfluorene (15 g, 54 mmol) dissolved in Et2O (100 mL) was added n-BuLi (5.8 mL of 10 M in hexanes, 58 mmol) at 0° C. The mixture was warmed to room temperature and stirred overnight. The anion solution was added to 2-butyl-6,6-diphenylpentafulvene (F-1) (16 g, 56 mmol) dissolved in Et2O (100 mL) at −78° C. in 5 minutes. The mixture was warmed to room temperature and stirred for 2 days. The reaction was quenched with a mixture of ice and 10% HCl 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 stirred in heptane to give a white solid. The solid was filtered, washed with heptane and dried under vacuum. A mixture of isomers for the desired product (18.7 g, 61.3% yield) was obtained as a white solid.

Workup

  1. temperatureThe mixture was warmed to room temperature
  2. stirringstirred for 2 days
  3. customThe reaction was quenched with a mixture of ice and 10% HCl 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. customto give a white solid
  10. filtrationThe solid was filtered
  11. washwashed with heptane
  12. customdried under vacuum

Sources & evidence

ORD record
ord-2f6a607662944eaf9f5d96f1c456ea22
Source dataset
uspto-grants-2014_01
Patent number
US08637691B2

Reaction notes

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