The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction.

The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction.
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在苯乙烯氧化羰基化反应的振荡模式下,温度对选择性的影响。

DOI:
10.1002/cphc.201700359
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发表时间:
2017-08-05
期刊:
Chemphyschem : a European journal of chemical physics and physical chemistry
影响因子:
--
通讯作者:
Novakovic K
Novakovic K
中科院分区:
其他
文献类型:
--
作者:
Parker J;Novakovic K

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在钯催化的苯乙炔氧化羰基化反应的振荡模式中,反应温度对产物选择性起主要作用。在40 °C下,(2 Z)-2-苯基-2-丁烯二酸二甲酯是主要产物,而在0 °C下,主要产物是5,5-二甲氧基-3-苯基-2(5 H)-呋喃酮。pH值振荡的发生与苯乙炔消耗速率和相关产物形成速率的增加相一致。在反应量热计中等温进行实验,以将反应物消耗和产物形成与pH振荡的发生和由反应释放的热相关联。单次振荡中pH下降幅度的增加与能量的增加相关,这表明单次振荡的这一部分与反应物消耗有关。基于这些观察,提供了负责产物形成的反应途径。
Reaction temperature plays a major role in product selectivity in the oscillatory mode of the palladium‐catalyzed phenylacetylene oxidative carbonylation reaction. At 40 °C, dimethyl (2Z)‐2‐phenyl‐2‐butenedioate is the major product whereas at 0 °C the major product is 5,5‐dimethoxy‐3‐phenyl‐2(5H)‐furanone. The occurrence of oscillations in pH coincides with an increase in the rate of phenylacetylene consumption and associated product formation. Experiments were performed isothermally in a reaction calorimeter to correlate reactant consumption and product formation with the occurrence of pH oscillations and the heat released by the reaction. An increase in the size of the pH drop in a single oscillation correlates with an increase in energy, indicating that this section of a single oscillation relates to reactant consumption. Based on these observations, a reaction pathway responsible for product formation is provided.
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