Selective Oxidation in DSM: Innovative Catalysts and Technologies

Alsters, Paul L.; Aubry, Jean‐Marie; Bonrath, Werner; Daguenet, C.; Hans, Michael; Jary, Walther; Létinois, Ulla; Nardello‐Rataj, Véronique; Netscher, Thomas; Parton, Rudy F.; Schütz, Jan; Soolingen, Jaap Van; Tinge, Johan Thomas; Wüstenberg, Bettina

doi:10.1142/9781848167513_0016

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“…At 115 °C/11 bar O 2 and with a Pd(OAc) 2 loading of 0.5 mol % as in the above experiments, we then varied the amount of CF 3 CO 2 H relative to added Pd(OAc) 2 from 0 to 50 equivalents (Table S6). In line with our earlier findings, at this high O 2 pressure, the collective biaryl yield benefits from the addition of up to 2 equivalents of a strong carboxylic acid such as CF 3 CO 2 H. More CF 3 CO 2 H decreases both the yield and regioselectivity without affecting the chemoselectivity significantly. With 2 equivalents of CF 3 CO 2 H, the collective biaryl yield reached 26 % with a regio‐ and chemoratio of 5.7 and 6.1, respectively…”

Section: Resultssupporting

confidence: 91%

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Palladium‐Catalyzed Cross‐Dehydrogenative Coupling of o‐Xylene: Evidence of a New Rate‐Limiting Step in the Search for Industrially Relevant Conditions

Álvarez‐Casao

Slagmaat²,

Verzijl³

et al. 2018

ChemCatChem

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An efficient cross‐dehydrogenative coupling of o‐xylene under neat conditions, which brings important industrial benefits towards the synthesis of a monomer used in polyimide resins, is reported. The catalyst based on the combination of Pd/N ligand/carboxylate=1:1:2 does not require a Cu cocatalyst and proceeds at 11 bar of O2 pressure. Evaluation of the deuterium kinetic isotope effect (KIE) provides evidence for three different rate‐determining steps, which depend on the reaction conditions (medium, temperature). Under the reported neat conditions, the dissociation of a carboxylate‐bridged dimer to generate a more reactive monometallic Pd species is proposed to be the rate‐limiting step.

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Section: Resultssupporting

confidence: 91%

“…The results of our search for an aerobic CDC catalyst system in neat o ‐xylene have been published in patents filed in 2015 and 2016 . An important finding disclosed in the first patent is the use of a palladium carboxylate catalyst in the presence of 1 equivalent of an N‐donor ligand, such as pyridine.…”

Section: Introductionmentioning

confidence: 99%