L. Wilczek, J. Kennedy
1987
Citations
0
Influential Citations
16
Citations
Journal
Polymer Bulletin
Abstract
SummaryQuantitative electrophilic allylation of 2,4,4-trimethyl-2-chloropentane (TMP-Cl) a molecule which closely mimics the tert-chlorine termini of $$\mathop - \limits^t Cl - PIB - \mathop - \limits^t Cl$$ by allyltrimethylsilane (AllylSiMe3) has been accomplished and the product 4,4,6,6-tetramethyl-1-heptene (TMP-allyl), a new organic compound, has been characterized by1H NMR spectroscopy. The synthesis was carried out by the use of Et2AlCl or TiCl4 using CH2Cl2 or CH3Cl or CH2Cl2-C6H14 solvent systems in the range from −70 to 0°C. The allylation efficiency sequence of the Lewis acids studied was: Et2AlCl > TiCl4 > SnCl4 ≫ BCl3. Varying the temperature from −70° to 20°C moderately affected the conversions with lower temperatures being preferable. A dramatic solvent effect was observed: While in the presence of 30% CH2Cl2 both allylation efficiency and rate were very high, in hexanes allylation was strongly retarded. Vinyltrimethylsilane (VinylSiMe3), a potential vinylating agent, was inactive under the same conditions.