Gas phase acetoxylation of 1,3-butadiene over palladium catalysts

Exploring structure activity relationships in the acetoxylation of small olefins

“…Although the gas phase acetoxylation of butadiene has not yet reached the stage of an established chemical process, stimulating results were obtained from several groups [4][5][6]. The typical challenges that are reported are that mainly the mono-acetoxylated product is obtained and high selectivities to products of value can only be obtained at low conversions up to 5%, with selectivities dropping sharply beyond that threshold [7][8][9][10][11]. This was an incentive for us to look for catalyst systems and process conditions that would give new insight in the gas phase diacetoxalation by (a) systematically investigating the traditional and new compositions and dopants over a wide compositional range and (b) a broad variation for the feed parameters employed.…”

Acetoxylation of Ethylene

“…According to Shinohara [68,69], 1,4diacetoxy-but-2-ene can be produced via acetoxylation of 1,3-butadiene in the gas phase, using palladium antimony catalysts doped with vanadium and potassium acetate supported on a silica alumina calcined at 1200 • C. Antimony is found to alloy with palladium, and the homogeneously distributed vanadium(IV) species are attributed to activate oxygen via a Mars-van Krevelen mechanism [70], thus quasi-playing a similar role as copper in the classical Wacker reaction.…”

“…However, its (potential) precursor 1-acetoxybutadiene and its competing second-step product 3,4-diacetoxy-but-1-ene are also observed [68,69]. However, its (potential) precursor 1-acetoxybutadiene and its competing second-step product 3,4-diacetoxy-but-1-ene are also observed [68,69].…”