Selective synthesis of isobutene trimers and hexamers with oxo acid catalysts

The reaction of isobutene (IB) with its dimers (IB₂) catalyzed by CF₃SO₃H yielded isobutene trimers (IB₃) in high yield in nonpolar solvents at 0°C. The initial feed of isobutene, in the presence of equimolar IB₂ or more, was selectively converted into IB₃ without loss or accumulation of IB₂. After complete consumption of the isobutene, however, the remaining IB₂ rapidly dimerized to isobutene tetramers (IB₄). ¹³C-NMR analysis of the products showed that the IB₃ was formed via addition of the t-butyl cation (protonated isobutene to 2,4,4-trimethyl-1-pentene (an IB₂ isomer); the trimer fraction was free from isomers arising from addition of the t-butyl cation to 2,4,4-trimethyl-2-pentene (another IB₂ isomer) or addition of the IB₂ cation to isobutene. The IB₃ thus obtained was further oligomerized with CF₃SO₃H catalyst in nonpolar media in the range of 0 to ?25°C to give a mixture of IB₅, IB₆, and IB₇ in high yield. With EtAlCl₂ as catalyst, reaction of isobutene with IB₂ and oligomerization of IB₃ both resulted in products with a broad molecular weight distribution containing higher oligomers and complex hydrocarbons formed via cracking of the intermediate carbocations.