Christophe Grosjean - The influence of oscillations on product selectivity during the palladiumcatalysed phenylacetylene oxidative carbonylation reaction

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      Publication Details (including relevant citation   information):

      Novakovic, K.; Grosjean, C.; Scott, S. K.; Whiting, A.; Willis,   M. J.; Wright A. R. Phys. Chem. Chem. Phys., 2008, 10, 749‐753


      This paper reports on the influence of oscillations on product   selectivity as well as the dynamics

      of product formation during the palladium-catalysed   phenylacetylene oxidative carbonylation

      reaction in a catalytic system (PdI2, KI, Air, NaOAc in   methanol). The occurrence of the pH

      oscillations is related to PdI2 granularity and the initial pH   drop after phenylacetylene addition.

      To achieve pH and reaction exotherm oscillations regulation of   the amount of PdI2 is required,

      ensuring that the initial pH does not fall significantly below 1   after phenylacetylene addition.

      Experiments in both oscillatory and non-oscillatory pH regimes   were performed in an HEL

      SIMULARt reaction calorimeter with the concentration–time   profiles measured using a

      GC-MS. It is demonstrated that when operating in an oscillatory   pH regime product formation

      may be suppressed until oscillations occur after which there is a   steep increase in the formation of

      Z-2-phenyl-but-2-enedioic acid dimethyl ester. When operating in   non-oscillatory pH mode the

      products are formed steadily over time with the main products   being Z-2-phenyl-but-2-enedioic

      acid dimethyl ester, 2-phenyl-acrylic acid methyl ester and   E-3-phenyl-acrylic acid methyl ester.

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