Hydrochloric Acid → (Cyclopentadienyl)(fluorenyl)methane

HRID 37595Notes

Reaction equation

HRID 37595 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 178418339Butyllithium2×

Product 1

HCID 131717798(Cyclopentadienyl)(fluorenyl)methane

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

A second batch of the cyclopentadienyl-type ligand, (fluorenyl)(cyclopentadienyl)methane was prepared as follows. A solution of 13.7 g (0.0824 moles) fluorene in 200 mL tetrahydrofuran (THF) was treated with (0.0826 moles) n-butyllithium at room temperature. After 14.5 hours, 10.00 g (0.0825 moles) solid 6-(dimethylamino)fulvene were added to the orange-brown solution and the mixture was stirred at room temperature for 8.5 hours. The mixture was then reacted with 6.50 g (0.171 moles) LiAlH4 and refluxed 15.5 hours. Then 0.0032 moles n-butyllithium was added and the mixture was stirred for 10 minutes. The mixture was hydrolysed with 500 g ice, 500 mL ether and 200 mL concentrated HCl. The aqueous phase was extracted 3 times with 300 mL ether. The ether extracts were combined and the ether evaporated. The solid residue was mixed with pentane and filtered over silica. The yield was 5.7 g (fluorenyl)(cyclopentadienyl)methane having a gas chromatographic purity of 98%.

Workup

  1. temperaturerefluxed 15.5 hours
  2. stirringthe mixture was stirred for 10 minutes
  3. extractionThe aqueous phase was extracted 3 times with 300 mL ether
  4. customthe ether evaporated
  5. additionThe solid residue was mixed with pentane
  6. filtrationfiltered over silica

Sources & evidence

ORD record
ord-8afc06b85f5646cf95502b99bf35dd1d
Source dataset
uspto-grants-1995_05
Patent number
US05420320

Reaction notes

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