A new general procedure for the Heck arylation of disubstituted olefins is described. This procedure allows, in many instances, the stereoselective synthesis of trisubstituted olefins. Trisubstituted olefins are easily accessible under mild reaction conditions using a new catalyst system consisting of dicyclohexylamine or methyl-(dicyclohexyl)amine and a phase-transfer catalyst. The choice of base was found to be crucial for the rate and stereoselectivity of the Heck arylation reactions. This method is applicable to the coupling of both electron-deficient and electron-rich aryl halides and displays good stereoselectivity and a high degree of functional group compatibility. Labeling studies indicate that the source of this selectivity is thermodynamic in nature.
Transparent films were prepared by cross‐linking polyunsaturated poly(ether carbonate)s obtained by the multicomponent polymerization of CO2, propylene oxide, maleic anhydride, and allyl glycidyl ether. Poly(ether carbonate)s with ABXBA multiblock structures were obtained by sequential addition of mixtures of propylene oxide/maleic anhydride and propylene oxide/allyl glycidyl ether during the polymerization. The simultaneous addition of both monomer mixtures provided poly(ether carbonate)s with AXA triblock structures. Both types of polyunsaturated poly(ether carbonate)s are characterized by diverse functional groups, that is, terminal hydroxy groups, maleate moieties along the polymer backbone, and pendant allyl groups that allow for versatile polymer chemistry. The combination of double bonds substituted with electron‐acceptor and electron‐donor groups enables particularly facile UV‐ or redox‐initiated free‐radical curing. The resulting materials are transparent and highly interesting for coating applications.
Provided is a concept of how the carbon content of CO/CO2-containing blast furnace gas (BFG) from steel production could be utilized in a sequence of selective chemical conversion steps to produce high value intermediates for the polymer industry.
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