A Kinetic Model for Toluene Oxidation Comprising Benzylperoxy Benzoate Ester as Reactive Intermediate in the Formation of Benzaldehyde

During the oxidation of toluene under semibatch conditions, the formation of benzyl alcohol is initially equal to the rate of formation of benzaldehyde. As the overall conversion increases the benzyl alcohol concentration at first decreases much faster than benzaldehyde, but this decrease slows down causing the benzyl alcohol concentration to reduce to zero only very slowly. To account for this phenomenon a new reaction pathway has been proposed where the formation of benzaldehyde out of benzylhydroperoxide is catalysed by benzoic acid. Incorporation of this new reaction in a model improves the description of benzyl alcohol concentration prophiles while maintaining good predictions for benzaldehyde and benzoic acid

A kinetic model for toluene oxidation comprising benzylperoxy benzoate ester as reactive intermediate in the formation of benzaldehyde

During the oxidation of toluene under semibatch conditions, the formation of benzyl alcohol is initially equal to the rate of formation of benzaldehyde. As the overall conversion increases the benzyl alcohol concentration at first decreases much faster than benzaldehyde, but this decrease slows down causing the benzyl alcohol concentration to reduce to zero only very slowly. To account for this phenomenon a new reaction pathway has been proposed where the formation of benzaldehyde out of benzylhydroperoxide is catalysed by benzoic acid. Incorporation of this new reaction in a model improves the description of benzyl alcohol concentration prophiles while maintaining good predictions for benzaldehyde and benzoic acid

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

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

Direct alkoxylation of organopalladium compounds based on a new type of C-O coupling; reactivity of organopalladium compounds towards molybdenum peroxides

Molybdenum peroxide (2) reacts with organopalladium compounds in alcoholic solvents to form alkoxylated products instead of products derived from oxygen insertion in the C@?Pd bond

Process for the deprotection of protected amines

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Mechanistic studies on the Mukaiyama epoxidation

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