Reaktion #65872

Reaktionsgleichung

LiAlH4

6-(dimethylamino)fulvene

HCl

fluorene

n-butyllithium

→

(fluorenyl)(cyclopentadienyl)methane

Lösungsmittel

ether

THF

tetrahydrofuran

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONwere added
2. 2
   workup.STIRRINGthis mixture was stirred for 16 hours
3. 3
   Temperaturrefluxed 5.5 hours
4. 4
   SonstigeThen the clear phase was separated
5. 5
   Extraktionwas extracted with ether
6. 6
   Trocknendried over sodium sulfate
7. 7
   Sonstigethe solvent was evaporated at 15° C
8. 8
   workup.ADDITIONThe solid crude product was mixed with pentane
9. 9
   Filtrationfiltered over silica gel
10. 10
    Einengenconcentrated in vacuo
11. 11
    Temperaturcooled to -10° C. to -25° C.
12. 12
    Sonstigeto produce light yellow crystals
13. 13
    SonstigeAfter a second recrystallization from pentane

Vorschrift

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.

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