The chemical behavior of terminally tert-butylated polyolefins
Dagmar Klein, Henning Hopf, Peter G Jones, Ina Dix, Ralf Hänel
TL;DR
This paper explores how different polyolefins react chemically, focusing on hydrogenation, bromine addition, epoxidation, and Diels–Alder reactions.
Contribution
The study reveals specific reactivity patterns of terminally tert-butylated polyolefins in various chemical reactions.
Findings
Terminal olefinic carbon atoms in oligoenes are preferentially attacked in bromine addition reactions.
Epoxidation of triene and tetraene with MCPBA and DMDO leads to distinct rearrangement and symmetrical epoxide products.
Diels–Alder reactions with NPTD and TCNE show increased reactivity with extended conjugated π-systems.
Abstract
The chemical behavior of various oligoenes 2 has been studied. The catalytic hydrogenation of diene 3 yielded monoene 4. Triene 7 was hydrogenated to diene 8, monoene 9 and saturated hydrocarbon 10. Bromine addition to 3 and 7 yielded the dibromides 17 and 18, respectively, i.e., the oligoene system has been attacked at its terminal olefinic carbon atoms. Analogously, the higher vinylogs 19 and 20 yielded the 1,8- and 1,10-bromine adduts 23 and 24, respectively, when less than 1 equivalent of bromine was employed. Treatment of tetraene 19 with excess bromine provided tetrabromide 25. In epoxidation reactions, both with meta-chloroperbenzoic acid (MCPBA) and dimethyldioxirane (DMDO) two model oligoenes were studied: triene 7 and tetraene 19. Whereas 7 furnished the rearrangement product 31 with MCPBA, it yielded the symmetrical epoxide 32 with DMDO. Analogously, 19 was converted to…
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Taxonomy
TopicsOrganic Chemistry Cycloaddition Reactions · Chemical Reaction Mechanisms · Inorganic and Organometallic Chemistry