Hydrochloric Acid → (Cyclopentadienyl)(fluorenyl)methane

HRID 37594Notes

Reaction equation

HRID 37594 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.C([Li])CCC.CN(C)[CH:21]=[C:22]1[CH:26]=[CH:25][CH:24]=[CH:23]1.[H-].[H-].[H-].[H-].[Li+].[Al+3].Cl>O1CCCC1.CCOCC>[C:1]1([CH2:21][CH:22]2[CH:26]=[CH:25][CH:24]=[CH:23]2)[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

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 6853FluoreneHCID 1365236-(Dimethylamino)fulveneHCID 21226445Aluminium lithium hydrideHCID 178418339Butyllithium

Product 1

HCID 131717798(Cyclopentadienyl)(fluorenyl)methane

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

The cyclopentadienyl-type ligand, (fluorenyl)(cyclopentadienyl)methane was prepared as follows. A solution of 13.72 g (0.08252 mol) fluorene in 150 mL tetrahydrofuran (THF) was treated with 51.6 mL (0.08252 moles) 1.6M n-butyllithium solution at room temperature. The mixture was stirred at room temperature for 6 hours and then 10.00 g (0.0825 moles) 6-(dimethylamino)fulvene suspended in 50 mL THF were added and this mixture was stirred for 16 hours. The mixture was then reacted with 6.27 g (0.1652 mol) LiAlH4 and refluxed 5.5 hours. The product was carefully hydrolysed with ice water, 500 mL ether, and HCl. Then the clear phase was separated and was extracted with ether, dried over sodium sulfate, and the solvent was evaporated at 15° C. The solid crude product was mixed with pentane, filtered over silica gel, concentrated in vacuo, and cooled to -10° C. to -25° C. to produce light yellow crystals. After a second recrystallization from pentane, the yield was 5.27 g (fluorenyl)(cyclopentadienyl)methane, or 88 percent. Gas chromatography (GC) analysis indicated 97 percent purity.

Workup

  1. additionwere added
  2. stirringthis mixture was stirred for 16 hours
  3. temperaturerefluxed 5.5 hours
  4. customThen the clear phase was separated
  5. extractionwas extracted with ether
  6. dry with materialdried over sodium sulfate
  7. customthe solvent was evaporated at 15° C
  8. additionThe solid crude product was mixed with pentane
  9. filtrationfiltered over silica gel
  10. concentrationconcentrated in vacuo
  11. temperaturecooled to -10° C. to -25° C.
  12. customto produce light yellow crystals
  13. customAfter a second recrystallization from pentane

Sources & evidence

ORD record
ord-21e3634d7cbf45cebf24d2d30d0f3588
Source dataset
uspto-grants-1995_05
Patent number
US05420320

Reaction notes

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