67693-94-1Relevant academic research and scientific papers
Telomerization of 1,3-Butadiene with Carbon Dioxide: A Highly Efficient Process for δ-Lactone Generation
Balbino, Jo?o M.,Dupont, Jairton,Bayón, J. Carles
, p. 206 - 210 (2017/12/07)
A very efficient and selective telomerization of 1,3-butadiene with CO2 that leads to the δ-lactone (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one) was obtained using palladium acetate and tris(p-methoxyphenyl)phosphine as a catalyst in the presence of p-hydroquinone, N,N-diisopropylethylamine, and acetonitrile. A high turnover number of 4500 with 96 % selectivity to the δ-lactone was obtained after 5 h reaction at 70 °C. The reaction was deactivated by the presence of different 1,3-dialkylimidazolium ionic liquids, possibly by the formation of stable and inactive palladium-imidazole-2-ylidene carbenes.
Copolymerization of carbon dioxide and butadiene via a lactone intermediate
Nakano, Ryo,Ito, Shingo,Nozaki, Kyoko
, p. 325 - 331 (2014/04/17)
Although carbon dioxide has attracted broad interest as a renewable carbon feedstock, its use as a monomer in copolymerization with olefins has long been an elusive endeavour. A major obstacle for this process is that the propagation step involving carbon dioxide is endothermic; typically, attempted reactions between carbon dioxide and an olefin preferentially yield olefin homopolymerization. Here we report a strategy to circumvent the thermodynamic and kinetic barriers for copolymerizations of carbon dioxide and olefins by using a metastable lactone intermediate, 3-ethylidene-6-vinyltetrahydro-2H- pyran-2-one, which is formed by the palladium-catalysed condensation of carbon dioxide and 1,3-butadiene. Subsequent free-radical polymerization of the lactone intermediate afforded polymers of high molecular weight with a carbon dioxide content of 33 mol% (29 wt%). Furthermore, the protocol was applied successfully to a one-pot copolymerization of carbon dioxide and 1,3-butadiene, and one-pot terpolymerizations of carbon dioxide, butadiene and another 1,3-diene. This copolymerization technique provides access to a new class of polymeric materials made from carbon dioxide.
PALLADIUM-CATALYZED REACTION OF BUTADIENE AND CARBON DIOXIDE
Behr, Arno,Juszak, Klaus-D.
, p. 263 - 268 (2007/10/02)
The selective syntheses of the δ-lactone 2-ethylidene-6-hepten-5-olide and of the γ-lactone 2-ethyl-2,4-heptadien-4-olide by the palladium-catalyzed reaction of carbon dioxide and butadiene are described.Mechanistic studies showed that the formation of the γ-lactone proceeds by a consecutive reaction via the δ-lactone.The products are accounted for in terms of a reaction path involving an allylic palladium carboxylate complex as a key intermediate.
