Quantitative syntheses of novel polyisobutylenes fitted with terminal primary Br, OH, NH2, and methacrylate termini

Efficient syntheses of novel polyisobutylenes (PIBs) fitted with CH2·CH2·CH2Br, or CH2·CH2·CH2OH or CH2·CH2·CH2NH2 or CH2·CH2·CH2OCOC(CH3)CH2 group are described. The key to the syntheses is the preparation of the CH2·CH2·CH2Br, by quantitative anti-Markovnikov hydrobromination of readily-available ally-terminated PIB. The PIB derivatives are obtained from the bromo intermediate, and the composition of the medium is critical for essentially quantitative conversions. The sketch summarizes the transformations and structures. Glissopal®, a commercially available PIB carrying ∼ 82% of the CH2C(CH3)CH2 end group, was also converted to the corresponding primary alcohol. The structures of the intermediates and derivatives were established by high resolution NMR spectroscopy. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]