Reaction #1285894

Reaction equation

water

2-Bromo-2-methyl propane

Sodium cyclopentadienide

sodium bromide

→

2-cyclopentadienyl-2-methyl propane

Solvents

THF

Conditions

Workup

1. 1
   workup.ADDITIONAfter complete addition
2. 2
   Otherthe THF solution was collected over anhydrous sodium sulfate
3. 3
   ExtractionThe aqueous layer was repeatedly extracted with diethyl ether
4. 4
   FiltrationFiltration

Procedure

2-Bromo-2-methyl propane (353.5 g, 2.582 mol, Aldrich) was transferred into a 2-1 reaction flask with side-arms at 5° C. Sodium cyclopentadienide (1290 cm3 of a 2.0M solution in THF, 2.582 mol, Aldrich) was slowly added. After complete addition, the reaction set-up was allowed to warm up to ambient temperature over 12 hours. Distilled water was added to dissolve the resulting sodium bromide and the THF solution was collected over anhydrous sodium sulfate. The aqueous layer was repeatedly extracted with diethyl ether and combined with the THF solution. Filtration afforded the crude 2-cyclopentadienyl-2-methyl propane (t-BuCp), the solvent was removed and the crude product was fractionally distilled to obtain the pure (t-BuCp), boiling point 125° C. A sample of the pure t-BuCp (42.81 g, 0.351 mol) and THF (400 cm3) were transferred into a 1-1 reaction flask equipped with a mechanical stirrer. n-Butyl lithium (223 cm3 of a 1.6M solution in hexanes, 0.357 mol, Aldrich) was added dropwise at ambient temperature. The mixture was vigorously stirred for 3 hours and the resulting solution of t-BuC5H4 -Li+ was slowly added to a suspension of ZrCl4 (40.78 g, 0.175 mol) in THF (100 cm3) at -78° C. After complete addition of the lithiated salt, stirring continued and the reaction slowly warmed up to ambient temperature over 12 h. The solvent was stripped off under reduced pressure and the crude product was Soxhlet extracted in toluene to yield crystals, after cooling, of (t-BuCp)2ZrCl2. FIGS. 1 and 2 show the 'H NMR traces (400 MHz) for Bis(i-PropylCyclopentadienyl) Zirconium Dichloride and Bis(t-ButylCyclopentadienyl) Zirconium Dichloride, respectively.

Source